Platinum-copper-tungsten fuel cell catalyst

ABSTRACT

A composition for use as a catalyst in, for example, a fuel cell, the composition comprising platinum, copper and tungsten, or an oxide, carbide and/or salt of one or more of platinum, copper and tungsten, wherein the sum of the concentrations of platinum, copper and tungsten, or an oxide, carbide and/or salt thereof, is greater than 90 atomic percent.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application60/641,494, filed Jan. 5, 2005, which is incorporated herein byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions which are useful ascatalysts in fuel cell electrodes (e.g., electrocatalysts) and othercatalytic structures, and which comprise platinum, copper and tungsten.

2. Description of Related Technology

A fuel cell is an electrochemical device for directly converting thechemical energy generated from an oxidation-reduction reaction of a fuelsuch as hydrogen or hydrocarbon-based fuels and an oxidizer such asoxygen gas (in air) supplied thereto into a low-voltage direct current.Thus, fuel cells chemically combine the molecules of a fuel and anoxidizer without burning, dispensing with the inefficiencies andpollution of traditional combustion.

A fuel cell is generally comprised of a fuel electrode (anode), anoxidizer electrode (cathode), an electrolyte interposed between theelectrodes (alkaline or acidic), and means for separately supplying astream of fuel and a stream of oxidizer to the anode and the cathode,respectively. In operation, fuel supplied to the anode is oxidized,releasing electrons that are conducted via an external circuit to thecathode. At the cathode, the supplied electrons are consumed when theoxidizer is reduced. The current flowing through the external circuitcan be made to do useful work.

There are several types of fuel cells, including those havingelectrolytes of phosphoric acid, molten carbonate, solid oxide,potassium hydroxide, or a proton exchange membrane. A phosphoric acidfuel cell operates at about 160-220° C., and preferably at about190-200° C. This type of fuel cell is currently being used formulti-megawatt utility power generation and for co-generation systems(i.e., combined heat and power generation) in the 50 to several hundredkilowatts range.

In contrast, proton exchange membrane fuel cells use a solidproton-conducting polymer membrane as the electrolyte. Typically, thepolymer membrane is maintained in a hydrated form during operation inorder to prevent loss of ionic conduction which limits the operationtemperature typically to between about 70 and about 120° C., dependingon the operating pressure, and preferably below about 100° C. Protonexchange membrane fuel cells have a much higher power density thanliquid electrolyte fuel cells (e.g., phosphoric acid), and can varyoutput quickly to meet shifts in power demand. Thus, they are suited forapplications such as in automobiles and small-scale residential powergeneration where quick startup is a consideration.

In some applications (e.g., automotive) pure hydrogen gas is the optimumfuel; however, in other applications where a lower operational cost isdesirable, a reformed hydrogen-containing gas is an appropriate fuel. Areformed-hydrogen containing gas is produced, for example, bysteam-reforming methanol and water at 200-300° C. to a hydrogen-richfuel gas containing carbon dioxide. Theoretically, the reformate gasconsists of 75 vol % hydrogen and 25 vol % carbon dioxide. In practice,however, this gas also contains nitrogen, oxygen and, depending on thedegree of purity, varying amounts of carbon monoxide (up to 1 vol %).Although some electronic devices also reform liquid fuel to hydrogen, insome applications the conversion of a liquid fuel directly intoelectricity is desirable, as then high storage density and systemsimplicity are combined. In particular, methanol is an especiallydesirable fuel because it has a high energy density, a low cost, and isproduced from renewable resources.

For the oxidation and reduction reactions in a fuel cell to proceed atuseful rates, especially at operating temperatures below about 300° C.,electrocatalyst materials are typically provided at the electrodes.Initially, fuel cells used electrocatalysts made of a single metal,usually platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir),osmium (Os), silver (Ag) or gold (Au), because they are able towithstand the corrosive environment. In general, platinum is consideredto be the most efficient and stable single-metal electrocatalyst forfuel cells operating below about 300° C.

While the above-noted elements were first used in fuel cells in metallicpowder form, later techniques were developed to disperse these metalsover the surface of electrically conductive supports (e.g., carbonblack) to increase the surface area of the electrocatalyst. An increasein the surface area of the electrocatalyst in turn increases the numberof reactive sites, leading to improved efficiency of the cell.Nevertheless, fuel cell performance typically declines over time becausethe presence of electrolyte, high temperatures and molecular oxygendissolve the electrocatalyst and/or sinter the dispersed electrocatalystby surface migration or dissolution/re-precipitation.

Although platinum is considered to be the most efficient and stablesingle-metal electrocatalyst for fuel cells, it is costly. Additionally,an increase in electrocatalyst activity over platinum is desirable, ifnot necessary, for wide-scale commercialization of fuel cell technology.However, the development of cathode fuel cell electrocatalyst materialsfaces longstanding challenges. The greatest challenge is the improvementof the electrode kinetics of the oxygen reduction reaction. In fact,sluggish electrochemical reaction kinetics has preventedelectrocatalysts from attaining the thermodynamic reversible electrodepotential for oxygen reduction. This is reflected in exchange currentdensities of around 10⁻¹⁰ to 10⁻¹² A/cm² for oxygen reduction on, forexample, Pt at low and medium temperatures. A factor contributing tothis phenomenon includes the fact that the desired reduction of oxygento water is a four-electron transfer reaction and typically involvesbreaking a strong O—O bond early in the reaction. In addition, the opencircuit voltage is lowered from the thermodynamic potential for oxygenreduction due to the formation of peroxide and possible platinum oxidesthat inhibit the reaction. A second challenge is the stability of theoxygen electrode (cathode) during long-term operation. Specifically, afuel cell cathode operates in a regime in which even the most unreactivemetals are not completely stable. Thus, alloy compositions that containnon-noble metal elements may have a rate of corrosion that wouldnegatively impact the projected lifetime of a fuel cell. Corrosion maybe more severe when the cell is operating near open circuitconditions—the most desirable potential for thermodynamic efficiency.

Electrocatalyst materials at the anode also face challenges during fuelcell operation. Specifically, as the concentration of carbon monoxide(CO) rises above about 10 ppm in the fuel the surface of theelectrocatalyst can be rapidly poisoned. As a result, platinum (byitself) is a poor electrocatalyst if the fuel stream contains carbonmonoxide (e.g., reformed-hydrogen gas typically exceeds 100 ppm). Liquidhydrocarbon-based fuels (e.g., methanol) present an even greaterpoisoning problem. Specifically, the surface of the platinum becomesblocked with the adsorbed intermediate, carbon monoxide (CO). It hasbeen reported that H₂O plays a key role in the removal of such poisoningspecies in accordance with the following reactions:Pt+CH₃OH→Pt—CO+4H⁺+4e⁻  (1);Pt+H₂O→Pt—OH+H⁺+e⁻  (2); andPt—CO+Pt—OH→2Pt+CO₂+H⁺+e⁻  (3).As indicated by the foregoing reactions, the methanol is adsorbed andpartially oxidized by platinum on the surface of the electrode (1).Adsorbed OH, from the hydrolysis of water, reacts with the adsorbed COto produce carbon dioxide and a proton (2,3). However, platinum does notform OH species rapidly at the potentials where fuel cell electrodesoperate (e.g., 200 mV-1.5 V). As a result, step (3) is the slowest stepin the sequence, limiting the rate of CO removal, thereby allowingpoisoning of the electrocatalyst to occur. This applies in particular toa proton exchange membrane fuel cell which is especially sensitive to COpoisoning because of its low operating temperatures.

One approach for improving the cathodic performance of anelectrocatalyst during the reduction of oxygen and/or the anodicperformance during the oxidation of hydrogen or methanol is to employ anelectrocatalyst which is more active, corrosion resistant, and/or morepoison tolerant. For example, increased tolerance to CO has beenreported by alloying platinum and ruthenium at a 50:50 atomic ratio(see, D. Chu and S. Gillman, J. Electrochem. Soc. 1996, 143, 1685). Theelectrocatalysts proposed to-date, however, leave room for furtherimprovement.

BRIEF SUMMARY OF THE INVENTION

Briefly, therefore, the present invention is directed to a compositionfor use as a catalyst in oxidation or reduction reactions, in forexample fuel cells, the composition comprising platinum, copper andtungsten, or an oxide, carbide or salt of one or more of said platinum,copper and tungsten, wherein said composition has a body-centered-cubiclattice structure.

The present invention is further directed to a composition for use as acatalyst in oxidation or reduction reactions, in for example fuel cells,the composition comprising platinum, copper and tungsten, or an oxide,carbide or salt of one or more of said platinum, copper and tungsten,wherein said composition has a face-centered-cubic lattice structure.

The present invention is still further directed to a composition for useas a catalyst in oxidation or reduction reactions, in for example fuelcells, the composition comprising platinum, copper and tungsten, or anoxide, carbide or salt of one or more of said platinum, copper andtungsten, wherein the sum of the concentrations of platinum, copper andtungsten, or an oxide, carbide or salt thereof, is greater than 90atomic percent.

The present invention is still further directed to a composition for useas a catalyst in oxidation or reduction reactions, in for example fuelcells, the composition comprising platinum, copper and tungsten, or anoxide, carbide or salt of one or more of said platinum, copper andtungsten, wherein the concentration of tungsten, or an oxide, carbide orsalt thereof, is greater than 40 atomic percent.

The present invention is still further directed to a composition for useas a catalyst in oxidation or reduction reactions, in for example fuelcells, the composition comprising platinum, copper and tungsten, or anoxide, carbide or salt of one or more of said platinum, copper andtungsten, wherein the concentration of platinum, or an oxide, carbide orsalt thereof, is at least 30 atomic percent.

The present invention is still further directed to a composition for useas a catalyst in oxidation or reduction reactions, in for example fuelcells, the composition comprising platinum, copper and tungsten, or anoxide, carbide or salt of one or more of said platinum, copper andtungsten, wherein the concentration of copper, or an oxide, carbide orsalt thereof, is less than 20 atomic percent.

The present invention is still further directed to a composition for useas a catalyst in oxidation or reduction reactions, in for example fuelcells, the composition consisting essentially of platinum, copper andtungsten, or an oxide, carbide or salt of one or more of said platinum,copper and tungsten.

The present invention is still further directed to one or more of theforegoing catalyst compositions wherein said catalyst compositioncomprises an alloy of the recited metals, or alternatively wherein saidcatalyst consists essentially of an alloy of the recited metals.

The present invention is still further directed to a supportedelectrocatalyst powder for use in electrochemical reactor devices, thesupported electrocatalyst powder comprising any of the foregoingcatalyst compositions on electrically conductive support particles.

The present invention is still further directed to a fuel cellelectrode, the fuel cell electrode comprising electrocatalyst particlesand an electrode substrate upon which the electrocatalyst particles aredeposited, the electrocatalyst particles comprising any of the foregoingcatalyst compositions.

The present invention is still further directed to a fuel cellcomprising an anode, a cathode, a proton exchange membrane between theanode and the cathode, and any of the foregoing catalyst compositions,for the catalytic oxidation of a hydrogen-containing fuel or thecatalytic reduction of oxygen.

The present invention is still further directed to a method for theelectrochemical conversion of a hydrogen-containing fuel and oxygen toreaction products and electricity in a fuel cell comprising an anode, acathode, a proton exchange membrane therebetween, any of the foregoingcatalyst compositions, and an electrically conductive external circuitconnecting the anode and cathode. The method comprises contacting thehydrogen-containing fuel or the oxygen and any of the foregoing catalystcompositions to catalytically oxidize the hydrogen-containing fuel orcatalytically reduce the oxygen.

The present invention is still further directed to a fuel cellelectrolyte membrane, and/or a fuel cell electrode, having deposited ona surface thereof a layer of an unsupported catalyst composition, saidunsupported catalyst composition layer comprising any of the foregoingcatalyst compositions.

The present invention is still further directed to a method forpreparing one of the foregoing catalyst compositions from a catalystprecursor composition, said precursor composition comprising platinum,copper and tungsten, or an oxide, carbide or salt thereof. The processcomprises subjecting said precursor composition to conditions sufficientto remove a portion of the tungsten and/or copper present therein, suchthat the resulting catalyst composition comprises platinum, copper andtungsten, or an oxide, carbide or salt thereof, as set forth above.

In one preferred embodiment of the above-noted method, the catalystprecursor composition is contacted with an acidic solution to solubilizea portion of the tungsten and/or copper present therein. In analternative embodiment, this method comprises subjecting the catalystprecursor composition to an electrochemical reaction, wherein forexample a hydrogen-containing fuel and oxygen are converted to reactionproducts and electricity in a fuel cell comprising an anode, a cathode,a proton exchange membrane therebetween, the catalyst precursorcomposition, and an electrically conductive external circuit connectingthe anode and cathode. By contacting the hydrogen-containing fuel or theoxygen and the catalyst precursor composition, the hydrogen-containingfuel is oxidized and/or the oxygen is catalytically reduced. As part ofthis reaction, tungsten and/or copper are dissolved in situ from thecatalyst precursor composition.

The foregoing, as well as other features and advantages of the presentinvention, will become more apparent from the following description andaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a photograph of a TEM image of a carbon support with catalystnanoparticles deposited thereon, in accordance with the presentinvention.

FIG. 2 is an exploded, schematic structural view showing members of afuel cell.

FIG. 3 is cross-sectional view of the assembled fuel cell of FIG. 2.

FIG. 4 is a photograph of an electrode array comprising thin filmcatalyst compositions deposited on individually addressable electrodes,in accordance with the present invention.

It is to be noted that corresponding reference characters indicatecorresponding parts throughout the drawings.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a composition having catalyticactivity for use in, for example, oxidation and/or reduction reactionsof interest in a polyelectrolyte membrane fuel cell (e.g., anelectrocatalyst), the composition comprising, as further detailedherein, platinum, copper and tungsten, a portion of one or more of whichmay optionally be present in the form of a metal oxide or carbide orsalt. Advantageously and surprisingly, it has been discovered that thecatalyst compositions of the present invention may exhibit favorableelectrocatalytic activity while having reduced amounts of platinum, ascompared to, for example, a platinum standard.

In this regard it is to be noted that, in general, it is desirable, butnot essential, to reduce the cost of a catalyst composition to be usedin such reactions, particularly when used in fuel cells. One method ofreducing the cost of the catalyst composition is to decrease the amountof noble metals (such as platinum) used to produce it. Typically,however, as the concentrations of noble metals are decreased, catalystcompositions tend to become more susceptible to corrosion and/or theabsolute activity may be diminished. Thus, it is typically desirable toachieve the most activity per weight percent of noble metals (see, e.g.,End Current Density/Weight Fraction of Pt, as set forth in Tables A-E,infra). Preferably, this is accomplished without compromising, forexample, the life cycle of the fuel cell in which the catalystcomposition is placed. In addition to, or as an alternative to, reducingcost by limiting the noble metal concentration, a catalyst compositionof the present invention may be selected because it represents animprovement in corrosion resistance and/or activity compared to platinum(e.g., at least a 3 times increase in electrocatalytic activity comparedto platinum).

The present invention is thus directed to a composition that hascatalytic activity in oxidation and/or reduction reactions, and thatcomprises platinum, copper and tungsten, and optionally an oxide,carbide or salt thereof. It is to be noted that the catalyst compositionof the present invention may be in the form of an alloy of these metals,the composition for example consisting essentially of an alloycontaining these metals. Alternatively, the catalyst composition of thepresent invention may comprise these metals, a portion of which is inthe form of an alloy, the composition for example having alloy particlesinter-mixed with oxide, carbide or salt particles as a coating, as apseudo-support, and/or a simple mixture.

It is to be further noted that the catalyst composition of the presentinvention comprises an amount of platinum, copper and tungsten, andoptionally an oxide, carbide or salt thereof, which is sufficient foreach to play a role in the catalytic activity and/or crystallographicstructure of the catalyst composition. Stated another way, theconcentrations of platinum, copper and tungsten, and optionally anoxide, carbide or salt thereof, in the present catalyst composition aresuch that the presence of the each of these would not be considered animpurity therein. For example, when present, the concentrations of eachof platinum, copper and tungsten, and optionally an oxide, carbide orsalt thereof, are at least about 0.1, 0.5, 1 or even 2 atomic percent,wherein the sum of the concentrations thereof is greater than 90 atomicpercent, 92 atomic percent, 94 atomic percent, 96 atomic percent, 98atomic percent, or even 99 atomic percent.

In this regard it is to be still further noted that the catalystcomposition of the present invention may optionally consist essentiallyof platinum, copper and tungsten, including an oxide, carbide or saltthereof (e.g., impurities that play little, if any, role in thecatalytic activity and/or crystallographic structure of the catalyst maybe present to some degree), the concentrations of the metals, or anoxide, carbide or salt thereof, being within any one or more of theranges for an individual metal as set forth herein, or for thecombination of metals. Stated another way, the concentration of ametallic or non-metallic element other than platinum, copper andtungsten, or an oxide, carbide or salt thereof, may optionally notexceed what would be considered an impurity (e.g., less than 1, 0.5,0.1, or 0.01 atomic percent).

In view of the foregoing, it is to be understood that the catalystcomposition of the present invention may comprise, or consistessentially of, platinum, copper and tungsten metals. Alternatively, thecatalyst composition of the present invention may comprise, or consistessentially of, platinum, copper and tungsten, wherein a portion of oneor more of these components is in the form of oxides and/or carbidesand/or salts.

It is to be further noted that in one or more embodiments of the presentinvention, platinum, copper and/or tungsten may be substantially intheir metallic oxidation states. Stated another way, in one or moreembodiments of the present invention, the average oxidation state ofplatinum, copper and/or tungsten may be at or near zero. In oneparticular embodiment, the copper present in one or more of the catalystcompositions set forth herein has an average oxidation state that is ator near zero.

In view of the foregoing, it is to be understood that although in suchembodiments there may be portions of the catalyst composition whereinthe oxidation states of one or more of platinum, copper and tungsten aregreater than zero, the average oxidation states of these elementsthroughout the entire composition will be less than the lowest commonlyoccurring oxidation state for that particular element (e.g., the lowestcommonly occurring oxidation states for platinum, tungsten and copperare 2, 4 and 1, respectively). Therefore, the average oxidation state ofplatinum may be, for example, less than 2, 1.5, 1, 0.5, 0.1, or 0.01, oreven zero, wile the average oxidation state of tungsten may be, forexample, less than about 4, 3.5, 3, 2.5, 2, 1.5, 1, 0.5, 0.1, 0.01, oreven zero, and the average oxidation state of copper may be less than 1,0.5, 0.1, or 0.01, or even zero.

It is to be still further noted, however, that in an alternativeembodiment of the present invention, the platinum, copper and/ortungsten may not be substantially present in their metallic oxidationstates. Stated another way, in one or more embodiments of the presentinvention, the platinum, copper and/or tungsten in the catalystcomposition may have an average oxidation state that is greater thanzero (the platinum, copper and/or tungsten being present in thecatalyst, for example, as an oxide, carbide or salt, as previouslynoted). In fact, in one particular embodiment of the present invention,one or more of the catalyst compositions set forth herein comprises atungsten oxide (e.g., WO₂ or WO₃). Without being held to any particulartheory, and as further discussed herein below, it is believed thatunreacted tungsten may be present in one or more of the compositions ofthe present invention as tungsten oxide. Tungsten oxide may be presentdue to, at least in part, the use of certain tungsten precursors or theincomplete reduction of the tungsten precursors during the annealingprocedure. Unreacted tungsten may be present in the form of WO₂ afterannealing. Unreacted tungsten may also be present in the form of WO₃after a washing procedure, which is discussed further herein below.

1. Cataltst Compositions

A. Constituent Concentrations

As previously disclosed, the catalyst composition of the presentinvention comprises platinum, which may be in the form of for exampleplatinum metal, platinum oxide and/or platinum carbide and/or a platinumsalt. The concentration of platinum (e.g., platinum metal, platinumoxide, platinum carbide and/or platinum salt) in the present compositionis typically greater than about 10 atomic percent, and preferably isgreater than about 15 atomic percent, about 20 atomic percent, or evenabout 25 atomic percent, and is typically less than about 80 atomicpercent, about 75 atomic percent, about 70 atomic percent, about 65atomic percent, about 60 atomic percent, about 55 atomic percent, about50 atomic percent, about 45 atomic percent, or even about 40 atomicpercent. For example, the concentration of platinum metal, platinumoxide, platinum carbide and/or platinum salt may typically be in therange of about 10 to about 80 atomic percent, preferably about 15 toabout 70 atomic percent, more preferably about 20 to about 50 atomicpercent, or even more preferably from 25 to about 40 atomic percent.

In this regard it is to be noted, however, that the scope of the presentinvention is intended to encompass all of the various platinumconcentration range permutations possible herein, in view of theabove-noted maxima and minima.

The catalyst composition of the present invention also comprisestungsten, which may be in the form of for example tungsten metal,tungsten oxide, tungsten carbide and/or tungsten salt. The concentrationof tungsten (e.g., tungsten metal, tungsten oxide, tungsten carbideand/or tungsten salt) in the present composition may also vary within alarge compositional range. Typically, however, the concentration oftungsten (e.g., tungsten metal, tungsten oxide, tungsten carbide and/ortungsten salt) is greater than about 10 atomic percent, and preferablyis greater than about 20 atomic percent, about 30 atomic percent, about40 atomic percent, or even about 45 atomic percent, and is typicallyless than about 80 atomic percent, about 75 atomic percent, about 70atomic percent, about 65 atomic percent, or even about 60 atomicpercent. For example, the concentration of tungsten metal, tungstenoxide, tungsten carbide and/or tungsten salt may typically be in therange of about 10 to about 80 atomic percent, preferably about 20 toabout 75 atomic percent, more preferably about 30 to about 70 atomicpercent, more preferably about 40 to about 65 atomic percent, or morepreferably about 45 to about 60 atomic percent.

In this regard it is to be noted, however, that the scope of the presentinvention is intended to encompass all of the various tungstenconcentration range permutations possible herein, in view of theabove-noted maxima and minima.

The catalyst composition of the present invention also comprises copper,which may be in the form of for example copper metal, copper oxide,copper carbide and/or copper salt. The concentration of copper (e.g.,copper metal, copper oxide, copper carbide and/or copper salt) in thepresent composition may, like platinum and tungsten, also vary within alarge compositional range. Typically, however, the concentration ofcopper (e.g., copper metal, copper oxide, copper carbide, and/or coppersalt) is greater than about 1 atomic percent, and preferably is greaterthan about 2 atomic percent, about 3 atomic percent, about 4 atomicpercent, about 5 atomic percent, or even about 6 atomic percent, and istypically less than about 70 atomic percent, about 60 atomic percent,about 50 atomic percent, about 40 atomic percent, about 30 atomicpercent, or even about 20 atomic percent. For example, the concentrationof copper metal, copper oxide, copper carbide and/or copper salt maytypically be in the range of about 1 to about 60 atomic percent,preferably about 2 to about 50 atomic percent, more preferably about 3to about 40 atomic percent, more preferably about 4 to about 30 atomicpercent, or more preferably about 5 to about 20 atomic percent.

In this regard it is to be noted, however, that the scope of the presentinvention is intended to encompass all of the various copperconcentration range permutations possible herein, in view of theabove-noted maxima and minima.

It is to be further noted that the catalyst composition of the presentinvention may encompass any of the various combinations of platinum,copper and tungsten concentrations and/or ranges of concentrations setforth above without departing from its intended scope. For example, forthose embodiments wherein the catalyst composition of the presentinvention comprises platinum, copper and tungsten, each of which mayindependently be in the form of its metal, oxide, carbide, salt, or amixture thereof, the sum of the concentrations thereof may be greaterthan 90, 92 or even 95, atomic percent, and (i) the concentration ofplatinum (i.e., platinum metal, oxide, carbide and/or salt) may begreater than about 20 atomic percent and less than about 50 atomicpercent, or greater than about 25 atomic percent and less than about 40atomic percent; (ii) the concentration of tungsten (i.e., tungstenmetal, oxide, carbide and/or salt) may be greater than about 40 atomicpercent and less than about 80 atomic percent, or greater than about 45atomic percent and less than about 60 atomic percent; and, (iii) theconcentration of copper (i.e., copper metal, oxide, carbide and/or salt)may be greater than about 2 atomic percent and less than about 25 atomicpercent, or greater than about 5 atomic percent and less than about 20atomic percent.

The present invention may additionally, or alternatively, encompasscatalyst compositions wherein the sum of tungsten and copper (i.e.,tungsten or copper metal, oxide, carbide and/or salt) is at least 60atomic percent, 65 atomic percent, 70 atomic percent, 75 atomic percent,or even 80 atomic percent. For example, the present invention mayencompass catalyst compositions wherein: (i) the concentration ofplatinum (i.e., platinum metal, oxide, carbide and/or salt) is greaterthan about 30 atomic percent and less than about 40 atomic percent, theconcentration of copper (i.e., copper metal, oxide, carbide and/or salt)is greater than about 8 atomic percent and less than about 35 atomicpercent, and the concentration of tungsten (i.e., tungsten metal, oxide,carbide and/or salt) is greater than 30 atomic percent and less thanabout 55 atomic percent.

B. Atomic Ratios of Constituents

The catalyst compositions of the present invention may alternatively oradditionally be characterized in terms of atomic ratios between theconstituents. More specifically, it has been discovered that when usedas a catalyst one or more electrocatalytic properties (e.g. activity) ofthe compositions of the present invention may be controlled by, forexample, controlling the ratio of tungsten to copper. Specifically, ithas been discovered that activity may be altered (e.g., increased), infor example a catalyst composition wherein the concentration of platinumis less than about 50 atomic percent, by controlling the atomic ratio oftungsten to copper, in what ever forms each are independently present in(i.e., metal, oxide, carbide and/or salt), such that this ratio isgreater than about 1:1 (e.g., about 1.2:1, about 1.4:1, about 1.6:1,about 1.8:1 or more), with tungsten being in excess relative to copper.In such an embodiment, the atomic ratio of tungsten (e.g., metal, oxide,carbide and/or salt) to copper (e.g., metal, oxide, carbide and/or salt)may preferably be greater than about 2:1, more preferably greater thanabout 3:1, still more preferably greater than about 4:1, still morepreferably greater than about 5:1, still more preferably greater thanabout 6:1, still more preferably greater than about 7:1, still morepreferably greater than about 8:1, still more preferably greater thanabout 9:1, or still more preferably greater than about 10:1.

C. Compositional Drift

As has been reported elsewhere, subjecting a catalyst composition to anelectrocatalytic reaction (e.g., the operation of a fuel cell) maychange the composition by leaching one or more constituents (e.g.,tungsten and/or copper) from the catalyst (see, e.g., Catalysis for LowTemperature Fuel Cells Part 1: The Cathode Challenges, T. R. Ralph andM. P. Hogarth, Platinum Metals Rev., 2002, 46, (1), p. 3-14). Withoutbeing held to any particular theory, it is believed that this leachingeffect may potentially act to increase the activity of the catalyst byincreasing the surface area and/or by changing the surface compositionof the catalyst. In fact, the purposeful leaching of catalystcompositions after synthesis to increase the surface area has beendisclosed by Itoh et al. (see, e.g., U.S. Pat. No. 5,876,867 which isincorporated herein by reference).

Accordingly, it is to be noted that the concentrations, concentrationranges, and atomic ratios detailed herein for the catalyst compositionsof the present invention are intended to include the bulkstoichiometries, any surface stoichiometries resulting therefrom, andmodifications of the bulk and/or surface stoichiometries that result bysubjecting the catalyst compositions of the present invention to areaction (e.g., an electrocatalytic reaction) of interest.

D. Structural Characteristics

A catalyst composition of the present invention, such as Pt₃₅Cu₁₀W₅₅,may exhibit a variety of structural characteristics, as measured usingtechniques known in the art (e.g., XRD). For example, depending on theannealing conditions used to prepare the composition (as furtherdiscussed herein below), a face-centered-cubic (fcc) lattice structuremay be present that may exhibit a lattice constant smaller than Pt (see,e.g., sample HFC 1840 in Table E, annealed at about 675° C. for about 10hours), or a lattice constant larger than Pt (see, e.g., sample HFC1770, annealed at about 925° C. for about 2 hours). Without being heldto any particular theory, one possible explanation for this behaviorrelates to the respective metallic radii of Pt, Cu and W; the metallicradius of Cu is smaller than Pt, while the metallic radius of W islarger than Pt. For a given annealing time (e.g., some time betweenabout 2 and about 10 hours), at low annealing temperatures (e.g.,temperatures less than about 850° C., 800° C., 750° C., 700° C., or even650° C.) it is possible that Cu may react with Pt, resulting in alattice parameter smaller than Pt, while W remains largely unreacted.Conversely, for the same or similar annealing time, at high annealingtemperatures (e.g., temperature greater than about 650° C., 700° C.,750° C., 800° C. or even 850° C.) it is possible that both Cu and W mayreact with Pt, resulting in a lattice parameter that is larger than Pt.

Additionally, for the same composition, a body-centered-cubic (bcc)lattice structure may be present. It has been observed that the bcclattice structure may preferentially be formed using annealingconditions between those described above (e.g., between about 650° C.and 800° C., or about 700° C. and 750° C., and annealing time of about 5to about 10 hours). In other words, for certain catalyst compositions,the choice of annealing conditions may result in 3 different types ofXRD profiles.

Furthermore, it has been observed that the relative activity of acatalyst composition appears to show a dependence on the choice ofannealing conditions. In a general sense, it appears that a catalystcomposition, for example Pt₃₅Cu₁₀W₅₅, exhibiting a lattice constantlarger than Pt (that is, a sample that may have completely reacted, seee.g. sample 1770 or 1774), displays a lower relative activity than acatalyst of the same composition that exhibits a lattice constantsmaller than Pt (that is, a sample that had been annealed at lowertemperatures and has not completely reacted). In part, however, thiseffect may be related to the fact that the sample annealed at highertemperatures would possess larger particles. In between these tworanges, however, are the conditions in which the catalyst compositionexhibits the bcc lattice structure. It has been observed that sampleswhich are annealed in such a way as to exhibit the bcc latticestructure, particularly those which are tungsten-rich, appear to showthe highest relative activity.

In view of the foregoing, it is to be noted that the present inventionis additionally directed to a composition comprising platinum, copperand tungsten, or an oxide, carbide and/or salt of one or more of saidplatinum, copper and tungsten, wherein said composition has abody-centered-cubic lattice structure. Alternatively, the presentinvention is directed to a composition comprising platinum, copper andtungsten, or an oxide, carbide and/or salt of one or more of saidplatinum, copper and tungsten, wherein said composition has aface-centered-cubic lattice structure. Optionally, one or both of thesecompositions may be “tungsten-rich”.

In this regard it is to be noted that, as used herein, “tungsten-rich”refers to a composition wherein the concentration of tungsten, includingan oxide, carbide and/or salt thereof, is greater than the concentrationof either platinum, including an oxide, carbide and/or salt thereof, orcopper, including an oxide, carbide and/or salt thereof. Optionally,“tungsten-rich” may refer to a composition wherein the concentration oftungsten, including an oxide, carbide and/or salt thereof, exceeds thesum of the concentrations of platinum and copper, including oxides,carbides and/or salts thereof, and thus is the predominant componentthereof. For example, in one embodiment, “tungsten-rich” may refer to acomposition having a concentration of tungsten, including an oxide,carbide and/or salt thereof, that is greater than about 50 atomicpercent, about 55 atomic percent, about 60 atomic percent, about 65atomic percent, about 70 atomic percent, about 75 atomic percent, ormore (see, e.g., samples 1102 and 1172 to 1856).

2. Catalyst Composition Precursors—Washing/Leaching

With respect to the above-noted compositional drift that has beenobserved in use, it is to be further noted that, as illustrated by theresults presented in, for example, Table E herein (under the heading“Washed Powders”), the catalyst compositions of the present invention,once prepared, may optionally be subjected to a washing procedure, inorder to remove, for example tungsten and/or copper therefrom. Such aprocedure may be advantageous because it acts to remove at least aportion of the metal or metals that may otherwise leach from thecatalyst composition when in use (e.g., when used in a fuel cell), thusacting to extend the useful life of the device in which it is being used(by removing metals that would otherwise leach, and act ascontaminants).

The present invention is therefore additionally directed to a method forthe preparation of a catalyst composition from a catalyst precursorcomposition, said precursor composition comprising platinum, copper andtungsten. Generally speaking, the process comprises subjecting saidprecursor composition to conditions sufficient to remove a portion ofthe tungsten and/or copper present therein, such that a catalystcomposition, as set forth elsewhere herein is obtained (the catalystcomposition comprising, for example, platinum, copper and tungsten, aportion of each of which may be in the form of a metal, oxide, carbideand/or salt, wherein the sum of the concentrations thereof is greaterthan 90 atomic percent).

In one preferred embodiment of the above-noted method, the catalystprecursor composition is contacted with an acidic solution to wash orremove a portion of the tungsten and/or copper present therein out ofthe precursor. For example, a given weight of the catalyst precursorcomposition may be contacted with a quantity of a perchloric acid(HClO₄) solution (e.g., 1 M), heated (e.g., about 90 to about 95° C.)for a period of time (e.g., about 60 minutes), filtered, and thenrepeatedly washed with water. The precursor composition is preferablywashed a second time, the solid cake isolated from the first filtrationstep being collected and then subjected to substantially the samesequence of steps as previously performed, the cake being agitatedsufficiently to break it apart prior to and/or during the time spentheating the cake/acid solution mixture back up to the desiredtemperature. After the final filtration has been performed, the isolatedcake is dried (e.g., heated at about 90° C. for about 48 hours).

It is to be noted, however, that in an alternative embodiment thecatalyst precursor composition may be exposed to conditions commonwithin a fuel cell (e.g., immersion in an electrochemical cellcontaining an aqueous 0.5 M H₂SO₄ electrolyte solution maintained atroom temperature, such as described in Example 4, herein below), inorder to leach tungsten and/or copper from the precursor. Alternatively,the precursor may be directly subjected to an electrochemical reactionwherein, for example, a hydrogen-containing fuel and oxygen areconverted to reaction products and electricity in a fuel cell comprisingan anode, a cathode, a proton exchange membrane therebetween, thecatalyst precursor composition, and an electrically conductive externalcircuit connecting the anode and cathode. By contacting thehydrogen-containing fuel or the oxygen and the catalyst precursorcomposition, the hydrogen-containing fuel is oxidized and/or the oxygenis catalytically reduced. As part of this reaction, tungsten and/orcopper are thus dissolved in situ from the catalyst precursorcomposition. After this reaction has been allowed to continue for alength of time sufficient to obtain a substantially stable composition(i.e., a composition wherein the concentration of platinum, copperand/or tungsten remain substantially constant), the composition may beremoved from the cell and used as a catalyst composition in a futurefuel cell reaction of interest.

It is to be still further noted that the process for removing a portionof, for example, the tungsten and/or copper from the catalystcomposition precursor may be other than herein described withoutdeparting from the scope of the present invention. For example,alternative solutions may be used (e.g., HCF₃SO₃H, NAFION™, HNO₃, HCl,H₂SO₄, CH₃CO₂H), and/or alternative concentrations (e.g., about 0.05 M,0.1 M, 0.5 M, 1 M, 2 M, 3 M, 4 M, 5 M, etc.), and/or alternativetemperatures (e.g., about 25° C., 35° C., 45° C., 55° C., 65° C., 75°C., 85° C., etc.) and/or alternative washing times or durations (e.g.,about 5 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50minutes, 60 minutes or more), and/or alternative numbers of washingcycles (e.g., 1, 2, 3, 4, 5 or more), and/or alternative washingtechniques (e.g., those involving centrifugation, sonication, soaking,electrochemical techniques, or a combination thereof), and/oralternative washing atmospheres (e.g., ambient, oxygen-enriched, argon),as well as various combinations thereof (selected using means common inthe art).

3. Formation of Catalyst Composition Precursors Comprising/ConsistingEssentially of an Alloy

As previously noted, the catalyst composition, and/or the catalystcomposition precursor, of the present invention may consist essentiallyof an alloy of platinum, copper and tungsten. Alternatively, thecatalyst composition, and/or the catalyst composition precursor, of thepresent invention may comprise an alloy of platinum, copper andtungsten; that is, one or both of these may alternatively comprise analloy of these metals, and optionally one or more of these metals in anon-alloy form (e.g., a platinum, copper and/or tungsten salt and/oroxide and/or carbide).

Such alloys may be formed by a variety of methods. For example, theappropriate amounts of the constituents (e.g., metals) may be mixedtogether and heated to a temperature above the respective melting pointsto form a molten solution of the metals that is cooled and allowed tosolidify.

Typically, the catalyst compositions of the present invention, and/orthe precursors thereto, are used in a powder form to increase thesurface area, which in turn increases the number of reactive sites, andthus leads to improved efficiency of the cell in which the catalystcompositions are being used. Thus, a formed catalyst composition alloy,and/or the precursor thereto, may be transformed into a powder afterbeing solidified (e.g., by grinding), or during solidification (e.g.,spraying molten alloy and allowing the droplets to solidify). In thisregard it is to be noted, however, that in some instances it may beadvantageous to evaluate alloys for electrocatalytic activity in anon-powder form, such as a film, as further described and illustratedelsewhere herein (see, e.g., Examples 1 and 2, infra).

To further increase surface area and efficiency, a catalyst compositionalloy (i.e., a catalyst composition comprising or consisting essentiallyof an alloy), and/or the precursor thereto, may be deposited over thesurface of electrically conductive supports (e.g., carbon black) for usein a fuel cell. One method for loading a catalyst composition orprecursor alloy onto supports typically comprises depositingmetal-containing (e.g., platinum, copper and/or tungsten) compounds ontothe supports, converting these compounds to metallic form, and thenalloying the metals using a heat-treatment in a reducing atmosphere(e.g., an atmosphere comprising an inert gas such as argon and/or areducing gas such as hydrogen). One method for depositing thesecompounds involves the chemical precipitation thereof onto the supports.The chemical precipitation method is typically accomplished by mixingsupports and sources of the metal compounds (e.g., an aqueous solutioncomprising one or more inorganic metal salts) at a concentrationsufficient to obtain the desired loading of the catalyst composition, orprecursor thereto, on the supports, after which precipitation of thecompounds is initiated (e.g., by adding an ammonium hydroxide solution).The slurry is then typically filtered from the liquid under vacuum,washed with deionized water, and dried to yield a powder that comprisesthe metal compounds on the supports.

Another method for depositing the metal compounds comprises forming asuspension comprising a solution and supports suspended therein, whereinthe solution comprises a solvent portion and a solute portion thatcomprises the metal compound(s) being deposited. The suspension isfrozen to deposit (e.g., precipitate) the compound(s) on the supportparticles. The frozen suspension is then freeze-dried to remove thesolvent portion, leaving a freeze-dried powder comprising the supportsand the deposits of the metal compound(s) on the supports.

Since the process may involve sublimation of the solvent portion fromthe frozen suspension, the solvent portion of the solution in which thesupports are suspended preferably has an appreciable vapor pressurebelow its freezing point. Examples of such sublimable solvents that alsodissolve many metal-containing compounds and metals include water,alcohols (e.g., methanol, ethanol, etc.), acetic acid, carbontetrachloride, ammonia, 1,2-dichloroethane, N,N-dimethylformamide,formamide, etc.

The solution in which the supports are dispersed/suspended provides themeans for delivering the metal species which is to be deposited onto thesurfaces of the supports. The metal species may be the final desiredform, but in many instances it is not. If the metal species is not afinal desired form, the deposited metal species may be subsequentlyconverted to the final desired form. Examples of such metal species thatmay be subsequently converted include inorganic and organic metalcompounds such as metal halides, sulfates, carbonates, nitrates,nitrites, oxalates, acetates, formates, etc. Conversion to the finaldesired form may be made by thermal decomposition, chemical reduction,or other reaction. Thermal decomposition, for example, is brought aboutby heating the deposited metal species to obtain a different solidmaterial and a gaseous material. In general, as is known, thermaldecomposition of halides, sulfates, carbonates, nitrates, nitrites,oxalates, acetates, and formates may be carried out at temperaturesbetween about 200 and about 1,200° C.

If conversion of the deposited metal species to the final desired formis to occur, the deposited metal species is usually selected such thatany unwanted by-products from the conversion can be removed from thefinal product. For example, during thermal decomposition the unwanteddecomposition products are typically volatilized. To yield a finalproduct that is a metal alloy, the deposited metal species are typicallyselected so that the powder comprising the deposited metal species maybe reduced without significantly altering the uniformity of the metaldeposits on the surface of the supports and/or without significantlyaltering the particle size of the final powder (e.g., throughagglomeration).

Nearly any metal may be deposited onto supports by one or more of theprocesses noted herein, provided that the metal or compound containingthe metal is capable of being dissolved in a suitable medium (i.e., asolvent). Likewise, nearly any metal may be combined with, or alloyedwith, any other metal provided the metals or metal-containing compoundsare soluble in a suitable medium.

The solute portion may comprise an organometallic compound and/or aninorganic metal-containing compound as a source of the metal speciesbeing deposited. In general, organometallic compounds are more costly,may contain more impurities than inorganic metal-containing compounds,and may require organic solvents. Organic solvents are more costly thanwater and typically require procedures and/or treatments to controlpurity or negate toxicity. As such, organometallic compounds and organicsolvents are generally not preferred. Examples of appropriate inorganicsalts include Cu(NO₃)₂.2.5H₂O, and (NH₄)₁₀W₁₂O₄₁.5H₂O or(NH₄)₆W₁₂O₃₉.5H₂O. Such salts are highly soluble in water and, as aresult, water is often considered to be a preferred solvent. In someinstances, it is desirable for an inorganic metal-containing compound tobe dissolved in an acidic solution prior to being mixed with otherinorganic metal-containing compounds.

To form a catalyst alloy, or catalyst precursor alloy, having aparticular composition or stoichiometry, the amounts of the variousmetal-containing source compounds necessary to achieve that compositionare determined in view thereof. If the supports have a pre-depositedmetal, the loading of the pre-deposited metal on the supports istypically taken into account when calculating the necessary amounts ofmetal-containing source compounds. After the appropriate amounts of themetal-containing compounds are determined, the solution may be preparedby any appropriate method. For example, if all the selectedmetal-containing source compounds are soluble at the desiredconcentration in the same solvent at room temperature, they may merelybe mixed with the solvent. Alternatively, the suspending solution may beformed by mixing source solutions, wherein a source solution comprises aparticular metal-containing source compound at a particularconcentration. If, however, all of the selected compounds are notsoluble at the same temperature when mixed together (either as powdersin a solvent or as source solutions), the temperature of the mixture maybe increased to increase the solubility limit of one or more of thesource compounds so that the suspending solution may be formed. Inaddition to adjusting solubility with temperature, the stability of thesuspending solution may be adjusted, for example, by the addition of abuffer, by the addition of a complexing agent, and/or by adjusting thepH.

In addition to varying the amounts of the various metals to form alloyshaving different compositions, this method allows for a wide variationin the loading of the metal onto the supports. This is beneficialbecause it allows for the activity of a supported catalyst composition(e.g., an electrocatalyst powder) to be maximized. The loading may becontrolled in part by adjusting the total concentration of the variousmetals in the solution while maintaining the relative amounts of thevarious metals. In fact, the concentrations of the inorganicmetal-containing compounds may approach the solubility limit for thesolution. Typically, however, the total concentration of inorganicmetal-containing compounds in the solution is between about 0.01 M andabout 5 M, which is well below the solubility limit. In one embodiment,the total concentration of inorganic metal-containing compounds in thesolution is between about 0.1 M and about 1 M. Concentrations below thesolubility limit are used because it is desirable to maximize theloading of the supported catalysts without decreasing the surface areaof the metal deposits. Depending, for example, on the particularcomposition, the size of the deposits, and the uniformity of thedistribution of deposits on the supports, the loading may typically bebetween about 5 and about 60 weight percent. In one embodiment, theloading is between about 15 and about 45 or about 55 weight percent, orbetween about 20 and about 40 or about 50 weight percent. In anotherembodiment, the loading is about 20 weight percent, about 40 weightpercent, or about 50 weight percent.

The supports upon which the metal species (e.g., metal-containingcompound) is to be deposited may be of any size and composition that iscapable of being dispersed/suspended in the solution during the removalof heat to precipitate the metal species thereon. The maximum sizedepends on several parameters including agitation of the suspension,density of the supports, specific gravity of the solution, and the rateat which heat is removed from the system. In general, the supports areelectrically conductive and are useful for supporting catalyticcompounds in fuel cells. Such electrically conductive supports aretypically inorganic, for example, carbon supports. However, theelectrically conductive supports may comprise an organic material suchas an electrically conductive polymer (see, e.g., in U.S. Pat. No.6,730,350). Carbon supports may be predominantly amorphous or graphiticand they may be prepared commercially, or specifically treated toincrease their graphitic nature (e.g., heat treated at a hightemperature in vacuum or in an inert gas atmosphere) thereby increasingcorrosion resistance. Carbon black support particles may have aBrunauer, Emmett and Teller (BET) surface area up to about 2000 m²/g. Ithas been reported that satisfactory results are achieved using carbonblack support particles having a high mesoporous area, e.g., greaterthan about 75 m²/g (see, e.g., Catalysis for Low Temperature Fuel CellsPart 1: The Cathode Challenges, T. R. Ralph and M. P. Hogarth, PlatinumMetals Rev., 2002, 46, (1), p. 3-14). Experimental results to-dateindicate that a surface area of about 500 m²/g is preferred.

In another embodiment, the supports may have a pre-deposited materialthereon. For example, when the final composition of the deposits on thecarbon supports is a platinum alloy, it may be advantageous to use acarbon supported platinum powder. Such powders are commerciallyavailable from companies such as Johnson Matthey, Inc., of New Jerseyand E-Tek Div. of De-Nora, N.A., Inc., of Somerset, N.J. and may beselected to have a particular loading of platinum. The amount ofplatinum loading is selected in order to achieve the desiredstoichiometry of the supported metal alloy. Typically, the loading ofplatinum is between about 5 and about 60 weight percent. Preferably, theloading of platinum is between about 15 and 45 weight percent. The size(i.e., the maximum cross-sectional length) of the platinum deposits istypically less than about 20 nm. For example, the size of the platinumdeposits may be less than about 10 nm, 5 nm, 2 nm, or smaller;alternatively, the size of the platinum deposits may be between about 2and about 3 nm. Experimental results to-date indicate that a desirablesupported platinum powder may be further characterized by having aplatinum surface area of between about 150 and about 170 m²/g(determined by CO adsorption), a combined carbon and platinum surfacearea of between about 350 and about 400 m²/g (determined by N₂adsorption), and an average support size that is between about 100 andabout 300 nm.

The solution and supports are mixed according to any appropriate methodto form the dispersion/suspension, using means known in the art.Exemplary methods of mixing include magnetic stirring, insertion of astirring structure or apparatus (e.g., a rotor), shaking, sonication, ora combination of the foregoing methods. Provided that the supports canbe adequately mixed with the solution, the relative amounts of supportsand solution may vary over a wide range. For example, when preparingcarbon supported catalysts using an aqueous suspension comprisingdissolved inorganic metal-containing compounds, the carbon supportstypically comprise between about 1 and about 30 weight percent of thesuspension. Preferably, however, the carbon supports comprise betweenabout 1 and about 15 weight percent of the suspension, between about 1and about 10 weight percent of the suspension, between about 3 and about8 weight percent of the suspension, between about 5 and about 7 weightpercent of the suspension, or about 6 weight percent of the suspension.

In this regard it is to be noted that the above-referenced amounts ofcarbon supports in suspension may apply equally to other, non-carbonsupports noted herein, or which are known in the art.

The relative amounts of supports and solution may also be described interms of volumetric ratios. For example, the dispersion/suspension mayhave a volumetric ratio of support particles to solution or solvent thatis at least about 1:10; that is, the dispersion/suspension may have avolume of solution or solvent that is no more than about 10 times thevolume of support particles therein.

In this regard it is to be noted that specifying a minimum volumetricratio indicates that the volume of support particles may be increasedrelative to the volume of solution or solvent. As such, the volumetricratio of support particles to solution or solvent may more preferably beat least about 1:8, about 1:5, or even about 1:2. The volumetric ratiomay therefore range, for example, from about 1:2 to about 1:10, or fromabout 1:5 to about 1:8.

In one method of preparation, the solution and supports described orillustrated herein are mixed using sonication at a power and for aduration sufficient to form a dispersion/suspension in which the poresof the supports are impregnated with the solution and/or the supportsare uniformly distributed throughout the solution. If thedispersion/suspension is not uniformly mixed (i.e., the supports are notuniformly impregnated with the solution and/or the supports are notuniformly distributed throughout the solution), the deposits formed onthe supports will typically be non-uniform (e.g., the loading of themetal species may vary among the supports, the size of the deposits mayvary significantly on a support and/or among the supports, and/or thecomposition of the deposits may vary among the supports). Although auniform mixture, or distribution of supports in the solution, isgenerally preferred, there may be circumstances in which a non-uniformmixture, or distribution of supports in the solution, is desirable.

When a freeze-drying method of preparation is employed, typically theuniformity of the distribution of particles in the dispersion/suspensionis maintained throughout the removal of heat therefrom. This uniformitymay be maintained by continuing the mixing of the dispersion/suspensionas it is being cooled. The uniformity may, however, be maintainedwithout mixing by the viscosity of the dispersion/suspension. The actualviscosity needed to uniformly suspend the support particles depends inlarge part on the amount of support particle in thedispersion/suspension and the size of the support particles. To a lesserdegree, the necessary viscosity depends on the density of the supportparticles and the specific gravity of the solution. In general, theviscosity is typically sufficient to prevent substantial settling of thesupport particles as the heat is being removed from the suspension toprecipitate the deposits, and/or, if desired, until thedispersion/suspension is solidified by the freezing of the solution orsolvent. The degree of settling, if any, may be determined, for example,by examining portions of the solidified or frozen suspension. Typically,substantial settling would be considered to have occurred if theconcentration of supports in any two portions varies by more than about±10%. When preparing a carbon supported catalyst powder, or precursorsthereto, in accordance with the freeze-drying method, the viscosity ofthe suspension/dispersion is typically sufficient to prevent substantialsettling for at least about 4 minutes. In fact, the viscosity of thesuspension/dispersion may be sufficient to prevent substantial settlingfor at least about 10 minutes, at least about 30 minutes, at least about1 hour, at least about 6 hours, at least about 12 hours, at least about18 hours, or even up to about 2 days. Typically, the viscosity of thedispersion/suspension is at least about 5,000 mPa·s.

Heat is removed from the dispersion/suspension so that at least a partof the solute portion separates from the solvent portion and deposits(e.g., precipitates) a metal species/precipitated metal onto thesupports and/or onto any pre-existing deposits (e.g., a pre-depositedmetal and/or pre-deposited metal species formed, for example, byprecipitation of incompatible solutes). If the concentration of supportsin the suspension is sufficient (e.g., within the ranges set forthabove) and enough heat is removed, nearly all of the metal species to bedeposited is separated from the solvent portion to form deposits (e.g.,precipitates) comprising the metal species on the supports. In oneembodiment, the heat is removed to solidify or freeze thedispersion/suspension and form a composite comprising thesupports/particulate support with deposits comprising the metal speciesor a precipitated metal on the supports/particulate support, within amatrix of the solvent portion in a solid state. If the concentration ofthe solute portion in the solution exceeds the ability of the supportsto accommodate deposits of the metal species, some of the solute portionmay crystallize within the matrix. If this occurs, such crystals are notconsidered to be a supported powder.

In one embodiment of the present invention, the size of the deposits ofthe metal species is controlled such that the eventually formed depositsof the catalyst composition alloy, or precursor thereto, are of a sizesuitable for use as a fuel cell catalyst (e.g., no greater than about 20nm, about 10 nm, about 5 nm (50 Å), about 3 nm (30 Å), about 2 (20 Å)nm, in size or smaller). As set forth above, control of the alloydeposit size may be accomplished, at least in part, by maintaining awell-impregnated and uniformly distributed suspension throughout theremoval of heat from the system. Additionally, the control of thedeposit size may be accomplished by rapidly removing heat from thedispersion/suspension as the compound or compounds are depositing onsupports.

The rapid heat removal may be accomplished by cooling thedispersion/suspension from a temperature of at least about 20° C. to atemperature below the freezing point of the solvent at a rate of, forexample, at least about 20 ° C./minute. In order of increasingpreference, heat removal may comprise cooling the dispersion/suspensionat a rate of at least about 50, 60, 70, 80, 90, or 100 ° C./minute. Assuch, the dispersion/suspension may be cooled at a rate that is betweenabout 50 and about 100° C./minute, or at a rate that is between about 60and about 80° C./minute. Typically, removal of heat is at a rate thatallows for the temperature of the suspension to be reduced from atemperature such as room temperature (about 20° C.) or higher (e.g.,about 100° C.) to the freezing point of the solution or solvent within arelatively short period of time (e.g., not more than about 10, 5, or 3minutes).

The heat may be removed from the dispersion/suspension by anyappropriate method. For example, a container containing a volume of thedispersion/suspension may be placed within a refrigeration unit such asfreeze-dryer, a volume of dispersion/suspension may be contacted with acooled surface (e.g., a plate or container), a volume ofdispersion/suspension in a container may be immersed in, or otherwisecontacted with, a cryogenic liquid. Advantageously, the same containermay also be used during the formation of the dispersion and/or duringthe separation of solvent from deposited supports. In one embodiment acover is placed over an opening of the container. Although the cover maycompletely prevent the escape of any solid matter from the container,the cover preferably allows for a gas to exit the container whilesubstantially preventing the supports from exiting the container. Anexample of such a cover includes a stretchable film (e.g., PARAFILM)having holes that are, for example, less than about 500, 400, or 300 μmin size (maximum length across the hole).

In one embodiment the dispersion/suspension is cooled at a rate of atleast about 20° C./minute by immersing or contacting a containercontaining the dispersion/suspension in or with a volume of cryogenicliquid within a cryogenic container sized and shaped so that at least asubstantial portion of its surface is contacted with the cryogenicliquid (e.g., at least about 50, 60, 70, 80, or 90 percent of thesurface of the dispersion/suspension container). The cryogenic liquid istypically at a temperature that is at least about 20° C. below thefreezing point of the solvent. Examples of suitable cryogenic liquidstypically include liquid nitrogen, liquid helium, liquid argon, but evenless costly media may be utilized (for example, an ice water/hydrouscalcium chloride mixture can reach temperatures down to about −55° C.,an acetone/dry ice mixture can reach temperatures down to about −78° C.,and a diethyl ether/dry ice mixture can reach temperatures down to about−100° C.).

The container may be made of nearly any type of material. Generally, theselected material does not require special handling procedures, canwithstand repeated uses without structural failure (e.g., resistant tothermal shock), does not contribute impurities to the suspension (e.g.,resistant to chemical attack), and is thermally conductive. For example,plastic vials made from high density polyethylene may be used.

The supports having the deposits thereon may be separated from thesolvent portion by any appropriate method such as filtration,evaporation (e.g., by spray-drying), sublimation (e.g., freeze-drying),or a combination thereof. The evaporation or sublimation rate may beenhanced by adding heat (e.g., raising the temperature of the solvent)and/or decreasing the atmospheric pressure to which the solvent isexposed.

In one embodiment a frozen or solidified suspension is freeze-dried toremove the solvent portion therefrom. The freeze-drying may be carriedout in any appropriate apparatus, such as a LABCONCO FREEZE DRY SYSTEM(Model 79480). Intuitively, one of skill in the art would typicallymaintain the temperature of the frozen suspension below the meltingpoint of the solvent (i.e., the solvent is removed by sublimation), inorder to prevent agglomeration of the supports. The freeze-dryingprocess described or illustrated herein may be carried out under suchconditions. Surprisingly, however, it is not critical that the solventportion remain fully frozen. Specifically, it has been discovered that afree-flowing, non-agglomerated powder may be prepared even if thesolvent is allowed to melt, provided that the pressure within thefreeze-dryer is maintained at a level that the evaporation rate of theliquid solvent is faster than the melting rate (e.g., below about 0.2millibar, 0.000197 atm, or 20 Pa). Thus, there is typically not enoughsolvent in the liquid state to result in agglomeration of the supports.Advantageously, this can be used to decrease the time needed to removethe solvent portion. Removing the solvent portion results in afree-flowing, non-agglomerated supported powder that comprises thesupports/particulate support and deposits comprising one or more metalspecies or precipitated metals on the supports/particulate support.

To accomplish the conversion of the deposited compound to the desiredform of the metal therein, the powder is typically heated in a reducingatmosphere (e.g., an atmosphere containing hydrogen and/or an inert gassuch as argon) at a temperature sufficient to decompose the depositedcompound. The temperature reached during the thermal treatment istypically at least as high as the decomposition temperature(s) for thedeposited compound(s) and not so high as to result in degradation of thesupports and agglomeration of the supports and/or the catalyst deposits.Typically, the temperature is between about 60° C. and about 1100° C.,between about 100 and about 1000° C., between about 200 and about 800 °C., or between about 400 and about 600° C. Inorganic metal-containingcompounds typically decompose at temperatures between about 600 and1000° C.

The duration of the heat treatment is typically at least sufficient tosubstantially convert the deposited compounds to the desired state. Ingeneral, the temperature and time are inversely related (i.e.,conversion is accomplished in a shorter period of time at highertemperatures and vice versa). At the temperatures typical for convertingthe inorganic metal-containing compounds to an alloy set forth above,the duration of the heat treatment is typically at least about 30minutes (e.g., about 1, 2, 4, 6, 8, 10, 12 hours, or longer). Forexample, the duration may be between about 1 and about 14 hours, about 2and about 12 hours, or between about 4 and about 6 hours.

Referring to FIG. 1, a carbon supported catalyst alloy powder particle 1of the present invention, produced in accordance with the freeze-dryingmethod described or illustrated herein, comprises a carbon support 2 anddeposits 3 of the catalyst alloy on the support. A particle and a powdercomprising said particles may have a loading that is up to about 90weight percent. However, when a supported catalyst powder is used as afuel cell catalyst, the loading is typically between about 5 and about60 weight percent, and is preferably between about 15 and about 45 orabout 55 weight percent, or more preferably between about 20 and about40 or 50 weight percent (e.g., about 20 weight percent, 45 weightpercent, or about 50 weight percent). Increasing the loading to greaterthan about 60 weight percent does not typically result in an increase inthe activity. Without being held to a particular theory, it is believedthat excess loading covers a portion of the deposited metal and thecovered portion cannot catalyze the desired electrochemical reaction. Onthe other hand, the activity of the supported catalyst typicallydecreases significantly if the loading is below about 5 weight percent.

The freeze-dry method may be used to produce supported catalyst alloypowders that are heavily loaded with nanoparticle deposits of a catalystalloy that comprises one or more non-noble metals, wherein the depositshave a relatively narrow size distribution. For example, in oneembodiment the supported non-noble metal-containing catalyst alloypowder may have a metal loading of at least about 20 weight percent ofthe powder, an average deposit size that is no greater than about 10 nm,and a deposit size distribution in which at least about 70 percent ofthe deposits are within about 50 and 150 percent of the average depositsize. In another embodiment, the metal loading may preferably be betweenabout 20 and about 60 weight percent, and more preferably between about20 and about 40 weight percent.

The average size of the catalyst alloy deposits is typically no greaterthan about 5 nm (50 Å). Preferably, however, the average size of thecatalyst alloy deposits is no greater than about 3 nm (30 Å), 2 nm (20Å), or even 1 nm (10 Å). Alternatively, however, the average size of themetal alloy deposits may preferably be between about 3 nm and about 10nm, or between about 5 nm and about 10 nm. Additionally, the sizedistribution of the deposits is preferably such that at least about 80percent of the deposits are within about 75 and 125 percent of theaverage deposit size.

The freeze-dry method of preparing supported catalyst powders allows forimproved control of the stoichiometry of the deposits because thesuspension is preferably kept within a single container, the solution isnot physically separated from the supports (e.g., by filtration), andfreezing results in substantially all of the solute precipitating on thesupports. Additionally, the deposits tend to be isolated, small, anduniformly dispersed over the surface of the supports, thereby increasingthe overall catalytic activity. Still further, because filtering is notnecessary, extremely fine particles are not lost and the supportedcatalyst powders produced by this method tend to have a greater surfacearea and activity. Also, the act of depositing the metal species on thesupports is fast. For example, immersing a container of thedispersion/suspension in a cryogenic liquid may solidify thedispersion/suspension in about three to four minutes.

4. Unsupported Catalyst Compositions in Electrode/Fuel Cell Applications

It is to be noted that, in another embodiment of the present invention,a catalyst composition (e.g., the catalyst composition comprising orconsisting essentially of an alloy of the metal components), and/or theprecursor thereto, may be unsupported; that is, a catalyst compositionas set forth herein may be employed in the absence of support particles.More specifically, it is to be noted that in another embodiment of thepresent invention a catalyst composition comprising platinum, copper andtungsten, as defined herein, may be directly deposited (e.g., sputtered)onto, for example: (i) a surface of one or both of the electrodes (e.g.,the anode, the cathode or both), and/or (ii) one or both surfaces of apolyelectrolyte membrane, and/or (iii) some other surface, such as abacking for the membrane (e.g., carbon paper).

In this regard it is to be further noted that each constituent (e.g.,metal-containing compound) of the composition may be depositedseparately, each for example as a separate layer on the surface of theelectrode, membrane, etc. Alternatively, two or more constituents may bedeposited at the same time. Additionally, when the composition comprisesor consists essentially of an alloy of these metals, the alloy may beformed and then deposited, or the constituents thereof may be depositedand then the alloy subsequently formed thereon.

Deposition of the constituent(s) may be achieved using means known inthe art, including for example known sputtering techniques (see, e.g.,PCT Application No. WO 99/16137, or U.S. Pat. No. 6,171,721 which isincorporated herein by reference). Generally speaking, however, in oneapproach sputter-deposition is achieved by creating, within a vacuumchamber in an inert atmosphere, a voltage differential between a targetcomponent material and the surface onto which the target constituent isto be deposited, in order to dislodge particles from the targetconstituent material which are then attached to the surface of, forexample, an electrode or electrolyte membrane, thus forming a coating ofthe target constituent thereon. In one embodiment, the constituents aredeposited on a polymeric electrolyte membrane, including for example (i)a copolymer membrane of tetrafluoroethylene and perfluoropolyethersulfonic acid (such as the membrane material sold under the trademarkNAFION™), (ii) a perfluorinated sulfonic acid polymer (such as themembrane material sold under the trademark ACIPLEX), (iii) polyethylenesulfonic acid polymers, (iv) polyketone sulfonic acids, (v)polybenzimidazole doped with phosphoric acid, (vi) sulfonated polyethersulfones, and (vii) other polyhydrocarbon-based sulfonic acid polymers.

It is to be noted that the specific amount of each metal or constituentof the composition may be controlled independently, in order to tailorthe composition to a given application. In some embodiments, however,the amount of each deposited constituent, or alternatively the amount ofthe deposited catalyst (e.g., catalyst alloy), may be less than about 5mg/cm² of surface area (e.g., electrode surface area, membrane surfacearea, etc.), less than about 1 mg/cm², less than about 0.5 mg/cm², lessthan about 0.1 mg/cm², or even less than about 0.05 mg/cm². In otherembodiments, the amount of the deposited constituent, or alternativelythe amount of the deposited catalyst (e.g., catalyst alloy), may rangefrom about 0.5 mg/cm² to less than about 5 mg/cm², or from about 0.1mg/cm² to less than about 1 mg/cm².

It is to be further noted that the specific amount of each constituent,or the composition, and/or the conditions under which the constituent,or composition, are deposited, may be controlled in order to control theresulting thickness of the constituent, or composition, layer on thesurface of the electrode, electrolyte membrane, etc. For example, asdetermined by means known in the art (e.g., scanning electron microscopyor Rutherford back scattering spectrophotometric method), the depositedlayer of the constituent or composition may have a thickness rangingfrom several angstroms (e.g., about 2, 4, 6, 8, 10 Å or more) to severaltens of angstroms (e.g., about 20, 40, 60, 80, 100 Å or more), up toseveral hundred angstroms (e.g., about 200, 300, 400, 500 Å or more).Additionally, after all of the constituents have been deposited, andoptionally alloyed (or, alternatively, after the composition has beendeposited, and optionally alloyed), the layer of the composition of thepresent invention may have a thickness ranging from several tens ofangstroms (e.g., about 20, 40, 60, 80, 100 Å or more), up to severalhundred angstroms (e.g., about 200, 400, 600, 800, 1000, 1500 Å ormore). Thus, in different embodiments the thickness may be, for example,between about 10 and about 500 angstroms (Å), between about 20 and about200 angstroms (Å), and between about 40 and about 100 angstroms (Å).

It is to be still further noted that in embodiments wherein acomposition (or the constituents thereof) is deposited as a thin film onthe surface of, for example, an electrode or electrolyte membrane, thevarious concentrations of platinum, copper and tungsten therein may beas previously described herein. Additionally, in other embodiments, theconcentration of platinum, copper and tungsten in the composition may beother than as previously described.

5. Incorporation of the Composition in a Fuel Cell

The compositions of the present invention are particularly suited foruse as catalysts in proton exchange membrane fuel cells. As shown inFIGS. 2 and 3, a fuel cell, generally indicated at 20, comprises a fuelelectrode (anode) 22 and an air electrode/oxidizer electrode (cathode)23. In between the electrodes 22 and 23, a proton exchange membrane 21serves as an electrolyte and is usually a strongly acidic ion exchangemembrane, such as a perfluorosulphonic acid-based membrane. Preferably,the proton exchange membrane 21, the anode 22, and the cathode 23 areintegrated into one body to minimize contact resistance between theelectrodes and the proton exchange membrane. Current collectors 24 and25 engage the anode and the cathode, respectively. A fuel chamber 28 andan air chamber 29 contain the respective reactants and are sealed bysealants 26 and 27, respectively.

In general, electricity is generated by hydrogen-containing fuelcombustion (i.e., the hydrogen-containing fuel and oxygen react to formwater, carbon dioxide and electricity). This is accomplished in theabove-described fuel cell by introducing the hydrogen-containing fuel Finto the fuel chamber 28, while oxygen O (preferably air) is introducedinto the air chamber 29, whereby an electric current can be immediatelytransferred between the current collectors 24 and 25 through an outercircuit (not shown). Ideally, the hydrogen-containing fuel is oxidizedat the anode 22 to produce hydrogen ions, electrons, and possibly carbondioxide gas. The hydrogen ions migrate through the strongly acidicproton exchange membrane 21 and react with oxygen and electronstransferred through the outer circuit to the cathode 23 to form water.If the hydrogen-containing fuel F is methanol, it is preferablyintroduced as a dilute acidic solution to enhance the chemical reaction,thereby increasing power output (e.g., a 0.5 M methanol/0.5 M sulfuricacid solution).

To prevent the loss of ionic conduction in the proton exchangemembranes, these typically remain hydrated during operation of the fuelcell. As a result, the material of the proton exchange membrane istypically selected to be resistant to dehydration at temperatures up tobetween about 100 and about 120° C. Proton exchange membranes usuallyhave reduction and oxidation stability, resistance to acid andhydrolysis, sufficiently low electrical resistivity (e.g., <10 Ω·cm),and low hydrogen or oxygen permeation. Additionally, proton exchangemembranes are usually hydrophilic. This ensures proton conduction (byreversed diffusion of water to the anode), and prevents the membranefrom drying out thereby reducing the electrical conductivity. For thesake of convenience, the layer thickness of the membranes is typicallybetween 50 and 200 μm. In general, the foregoing properties are achievedwith materials that have no aliphatic hydrogen-carbon bonds, which, forexample, are achieved by replacing hydrogen with fluorine or by thepresence of aromatic structures; the proton conduction results from theincorporation of sulfonic acid groups (high acid strength). Suitableproton-conducting membranes also include perfluorinated sulfonatedpolymers such as NAFION™ and its derivatives produced by E. I. du Pontde Nemours & Co., Wilmington, Del. NAFION™ is based on a copolymer madefrom tetrafluoroethylene and perfluorovinylether, and is provided withsulfonic groups working as ion-exchanging groups. Other suitable protonexchange membranes are produced with monomers such as perfluorinatedcompounds (e.g., octafluorocyclobutane and perfluorobenzene), or evenmonomers with C—H bonds that do not form any aliphatic H atoms in aplasma polymer, which could constitute attack sites for oxidativebreakdown.

The electrodes of the present invention comprise the catalystcompositions of the present invention and an electrode substrate uponwhich the catalyst is deposited. In one embodiment, the composition isdirectly deposited on the electrode substrate. In another embodiment,the composition is supported on electrically conductive supports and thesupported composition is deposited on the electrode substrate. Theelectrode may also comprise a proton conductive material that is incontact with the composition. The proton conductive material mayfacilitate contact between the electrolyte and the composition, and maythus enhance fuel cell performance. Preferably, the electrode isdesigned to increase cell efficiency by enhancing contact between thereactant (i.e., fuel or oxygen), the electrolyte and the composition. Inparticular, porous or gas diffusion electrodes are typically used sincethey allow the fuel/oxidizer to enter the electrode from the face of theelectrode exposed to the reactant gas stream (back face), and theelectrolyte to penetrate through the face of the electrode exposed tothe electrolyte (front face), and reaction products, particularly water,to diffuse out of the electrode.

Preferably, the proton exchange membrane, electrodes, and catalystcomposition are in contact with each other. This is typicallyaccomplished by depositing the composition either on the electrode, oron the proton exchange membrane, and then placing the electrode andmembrane in contact. The composition of this invention can be depositedon either the electrode or the membrane by a variety of methods,including plasma deposition, powder application (the powder may also bein the form of a slurry, a paste, or an ink), chemical plating, andsputtering. Plasma deposition generally entails depositing a thin layer(e.g., between 3 and 50 μm, preferably between 5 and 20 μm) of acatalyst composition on the membrane using low-pressure plasma. By wayof example, an organic platinum compound such astrimethylcyclopentadienyl-platinum is gaseous between 10⁻⁴ and 10 mbarand can be excited using radio-frequency, microwaves, or an electroncyclotron resonance transmitter to deposit platinum on the membrane.According to another procedure, a catalyst powder, for example, isdistributed onto the proton exchange membrane surface and integrated atan elevated temperature under pressure. If, however, the amount ofcatalyst powder exceeds about 2 mg/cm², the inclusion of a binder suchas polytetrafluoroethylene is common. Further, the catalyst may beplated onto dispersed small support particles (e.g., the size istypically between 20 and 200 Å, and more preferably between about 20 and100 Å). This increases the catalyst surface area, which in turnincreases the number of reaction sites leading to improved cellefficiency. In one such chemical plating process, for example, a powderycarrier material such as conductive carbon black is contacted with anaqueous solution or aqueous suspension (slurry) of compounds of metalliccomponents constituting the alloy to permit adsorption or impregnationof the metallic compounds or their ions on or in the carrier. Then,while the slurry is stirred at high speed, a dilute solution of suitablefixing agent such as ammonia, hydrazine, formic acid, or formalin isslowly added drop-wise to disperse and deposit the metallic componentson the carrier as insoluble compounds or partly reduced fine metalparticles.

The loading, or surface concentration, of a composition on the membraneor electrode is based in part on the desired power output and cost for aparticular fuel cell. In general, power output increases with increasingconcentration; however, there is a level beyond which performance is notimproved. Likewise, the cost of a fuel cell increases with increasingconcentration. Thus, the surface concentration of composition isselected to meet the application requirements. For example, a fuel celldesigned to meet the requirements of a demanding application such as anextraterrestrial vehicle will usually have a surface concentration ofthe composition sufficient to maximize the fuel cell power output. Forless demanding applications, economic considerations dictate that thedesired power output be attained with as little of the composition aspossible. Typically, the loading of composition is between about 0.01and about 6 mg/cm². Experimental results to-date indicate that in someembodiments the composition loading is preferably less than about 1mg/cm², and more preferably between about 0.1 and 1 mg/cm².

To promote contact between the collector, electrode, composition andmembrane, the layers are usually compressed at high temperature. Thehousings of the individual fuel cells are configured in such a way thata good gas supply is ensured, and at the same time the product water canbe discharged properly. Typically, several fuel cells are joined to formstacks, so that the total power output is increased to economicallyfeasible levels.

In general, the catalyst compositions and fuel cell electrodes of thepresent invention may be used to electrocatalyze any fuel containinghydrogen (e.g., hydrogen and reformed-hydrogen fuels). Also,hydrocarbon-based fuels may be used including: saturated hydrocarbons,such as methane (natural gas), ethane, propane and butane; garbageoff-gas; oxygenated hydrocarbons, such as methanol and ethanol; fossilfuels, such as gasoline and kerosene; and, mixtures thereof.

To achieve the full ion-conducting property of proton exchangemembranes, in some embodiments suitable acids (gases or liquids) aretypically added to the fuel. For example, SO₂, SO₃, sulfuric acid,trifluoromethanesulfonic acid or the fluoride thereof, also stronglyacidic carboxylic acids such as trifluoroacetic acid, and volatilephosphoric acid compounds may be used (“Ber. Bunsenges. Phys. Chem.”,Volume 98 (1994), pages 631 to 635).

6. Fuel Cell Uses

As set forth above, the compositions of the present invention are usefulas catalysts in fuel cells that generate electrical energy to performuseful work. For example, the compositions may be used in fuel cellswhich are in: electrical utility power generation facilities;uninterrupted power supply devices; extraterrestrial vehicles;transportation equipment, such as heavy trucks, automobiles, andmotorcycles (see, Fuji et al., U.S. Pat. No. 6,048,633; Shinkai et al.,U.S. Pat. No. 6,187,468; Fuji et al., U.S. Pat. No. 6,225,011; andTanaka et al., U.S. Pat. No. 6,294,280); residential power generationsystems; mobile communications equipment such as wireless telephones,pagers, and satellite phones (see, Prat et al., U.S. Pat. No. 6,127,058and Kelley et al., U.S. Pat. No. 6,268,077); mobile electronic devicessuch as laptop computers, personal data assistants, audio recordingand/or playback devices, digital cameras, digital video cameras, andelectronic game playing devices; military and aerospace equipment suchas global positioning satellite devices; and, robots.

7. Definitions

Activity is defined as the maximum sustainable, or steady state, current(Amps) obtained from the electrocatalyst, when fabricated into anelectrode, at a given electric potential (Volts). Additionally, becauseof differences in the geometric area of electrodes, when comparingdifferent electrocatalysts, activity is often expressed in terms ofcurrent density (A/cm²).

An alloy may be described as a solid solution in which the solute andsolvent atoms (the term solvent is applied to the metal that is inexcess) are arranged at random, much in the same way as a liquidsolution may be described. If some solute atoms replace some of those ofthe solvent in the structure of the latter, the solid solution may bedefined as a substitutional solid solution. Alternatively, aninterstitial solid solution is formed if a smaller atom occupies theinterstices between the larger atoms. Combinations of the two types arealso possible. Furthermore, in certain solid solutions, some level ofregular arrangement may occur under the appropriate conditions resultingin a partial ordering that may be described as a superstructure. Iflong-range ordering of atoms occurs, the alloy may be described ascrystallographically ordered, or simply ordered. These alloys may havecharacteristics that may be distinguishable through characterizationtechniques such as XRD. Significant changes in XRD may be apparent dueto changes in symmetry. Although the global arrangement of the metalatoms may be similar in the case of a solid solution and an orderedalloy, the relationship between the specific locations of the metal Aand metal B atoms is now ordered, not random, resulting in differentdiffraction patterns. Further, a homogeneous alloy is a single compoundcomprising the constituent metals. A heterogeneous alloy comprises anintimate mixture of individual metals and/or metal-containing compounds.An alloy, as defined herein, is also meant to include materials whichmay comprise elements which are generally considered to be non-metallic.For example, some alloys of the present invention may comprise oxygenand/or carbon in an amount that is generally considered to be a low orimpurity level (see, e.g., Structural Inorganic Chemistry, A. F. Wells,Oxford University Press, 5th Edition, 1995, chapter 29).

8. EXAMPLES Example 1 Forming Catalysts on Individually AddressableElectrodes

The catalyst compositions set forth in Tables A-D, infra, were preparedusing the combinatorial techniques disclosed in Warren et al., U.S. Pat.No. 6,187,164; Wu et al., U.S. Pat. No. 6,045,671; Strasser, P., Gorer,S. and Devenney, M., Combinatorial Electrochemical Techniques For TheDiscovery of New Fuel-Cell Cathode Materials, Nayayanan, S. R.,Gottesfeld, S. and Zawodzinski, T., eds., Direct Methanol Fuel Cells,Proceedings of the Electrochemical Society, New Jersey, 2001, p. 191;and Strasser, P., Gorer, S. and Devenney, M., CombinatorialElectrochemical Strategies For The Discovery of New Fuel-Cell ElectrodeMaterials, Proceedings of the International Symposium on Fuel Cells forVehicles, 41st Battery Symposium, The Electrochemical Society of Japan,Nagoya 2000, p. 153. For example, an array of independent electrodes(with areas of between about 1 and 3 mm²) was fabricated on inertsubstrates (e.g., glass, quartz, sapphire, alumina, plastics, andthermally treated silicon). The individual electrodes were locatedsubstantially in the center of the substrate, and were connected tocontact pads around the periphery of the substrate with wires. Theelectrodes, associated wires, and contact pads were fabricated from aconducting material (e.g., titanium, gold, silver, platinum, copper orother commonly used electrode materials).

Specifically, the catalyst compositions set forth in Tables A-D wereprepared using a photolithography/RF magnetron sputtering technique (GHzrange) to deposit a thin film of the catalysts on arrays of 64individually addressable electrodes. A quartz insulating substrate wasprovided and photolithographic techniques were used to design andfabricate the electrode patterns on it. By applying a predeterminedamount of photoresist to the substrate, photolyzing pre-selected regionsof the photoresist, removing those regions that have been photolyzed(e.g., by using an appropriate developer), depositing a layer oftitanium about 500 nm thick using RF magnetron sputtering over theentire surface and removing predetermined regions of the depositedtitanium (e.g. by dissolving the underlying photoresist), intricatepatterns of individually addressable electrodes were fabricated on thesubstrate.

Referring to FIG. 4, the fabricated array 40 consisted of 64individually addressable electrodes 41 (about 1.7 mm in diameter)arranged in an 8×8 square that were isolated from each other (byadequate spacing) and from the substrate 44 (fabricated on an insulatingsubstrate), and whose interconnects 42 and contact pads 43 wereinsulated from the electrochemical testing solution (by hardenedphotoresist or other suitable insulating material).

After the initial array fabrication and prior to deposition of thecatalyst for screening, a patterned insulating layer covering the wiresand an inner portion of the peripheral contact pads was deposited,leaving the electrodes and the outer portion of the peripheral contactpads exposed (preferably approximately half of the contact pad iscovered with this insulating layer). Because of the insulating layer, itis possible to connect a lead (e.g., a pogo pin or an alligator clip) tothe outer portion of a given contact pad and address its associatedelectrode while the array is immersed in solution, without having toworry about reactions that can occur on the wires or peripheral contactpads. The insulating layer was a hardened photoresist, but any othersuitable material known to be insulating in nature could have been used(e.g., glass, silica, alumina, magnesium oxide, silicon nitride, boronnitride, yttrium oxide, or titanium dioxide).

Following the creation of the titanium electrode array, a steel maskhaving 64 holes (1.7 mm in diameter) was pressed onto the substrate toprevent deposition of sputtered material onto the insulating resistlayer. The deposition of the catalyst was also accomplished using RFmagnetron sputtering and a two shutter masking system as described by Wuet al. which enable the deposition of material onto 1 or more electrodesat a time. Each individual thin film catalyst was created by a superlattice deposition method. For example, when preparing a catalystcomposition consisting essentially of metals M1, M2 and M3, each isdeposited onto an electrode, and partially or fully alloyed with theother metals thereon. More specifically, first a metal M1 sputter targetis selected and a thin film of M1 having a defined thickness isdeposited on the electrode. This initial thickness is typically fromabout 3 to about 12 Å. After this, metal M2 is selected as the sputtertarget and a layer of M2 is deposited onto the layer of M1. Thethickness of M2 layer is also from about 3 to about 12 Å. Thethicknesses of the deposited layers are in the range of the diffusionlength of the metal atoms (e.g., about 10 to about 30 Å) which allowsin-situ alloying of the metals. Then, a layer of M3 is deposited ontothe M1-M2 alloy forming a M1-M2-M3 alloy film. As a result of the threedeposition steps, an alloy thin film (9-36 Å thickness) of the desiredstoichiometry is created. This concludes one deposition cycle. In orderto achieve the desired total thickness of a catalyst material,deposition cycles are repeated as necessary which results in thecreation of a super-lattice structure of a defined total thickness(typically about 700 Å). Although the number, thickness (stoichiometry)and order of application of the individual metal layers may bedetermined manually, it is desirable to utilize a computer program todesign an output file which contains the information necessary tocontrol the operation of the sputtering device during the preparation ofa particular library wafer (i.e., array). One such computer program isthe LIBRARY STUDIO software available from Symyx Technologies, Inc. ofSanta Clara, Calif. and described in European Patent No. 1080435 B1. Thecompositions of several as-sputtered alloys were analyzed using ElectronDispersive Spectroscopy (EDS) to confirm that they were consistent withdesired compositions (chemical compositions determined using EDS arewithin about 5% of the actual composition).

Arrays were prepared to evaluate the specific alloy compositions setforth in Tables A-D, below. Each table had one electrode that consistedessentially of platinum, which served as an internal standard for thescreening of the alloys on that array.

TABLE A [Lib. 130758] End Current End Current Density Density perRelative (Absolute Weight Activity Electrode Activity) Fraction ofCompared Cu Pt W Number mA/cm² Pt mA/cm² to Internal Pt at % at % at %34 −1.90 −4.01 2.30 20 40 40 1 −1.54 −2.76 1.85 40 40 20 33 −0.85 −1.211.03 20 60 20 56 −0.83 −0.83 1.00 0 100 0 2 −0.02 −0.07 0.02 40 20 40

TABLE B [Lib. 133815] End Current End Current Density Density perRelative (Absolute Weight Activity Electrode Activity) Fraction ofCompared Cu Pt W Number mA/cm² Pt mA/cm² to Internal Pt at % at % at %34 −1.25 −2.63 2.17 20 40 40 56 −0.58 −0.58 1.00 0 100 0 1 −0.56 −1.000.96 40 40 20 33 −0.53 −0.75 0.92 20 60 20 2 −0.09 −0.31 0.15 40 20 40

TABLE C [Lib. 137564] End Current End Current Density Density perRelative (Absolute Weight Activity Electrode Activity) Fraction ofCompared Cu Pt W Number mA/cm² Pt mA/cm² to Internal Pt at % at % at % 1−0.67 −0.96 1.57 20 60 20 17 −0.57 −0.66 1.33 10 80 10 25 −0.43 −0.431.00 0 100 0

TABLE D [Lib. 140150] End Current End Current Density Density perRelative (Absolute Weight Activity Electrode Activity) Fraction ofCompared Cu Pt W Number mA/cm² Pt mA/cm² to Internal Pt at % at % at % 3−4.91 −14.70 3.90 10 30 60 21 −4.76 −13.27 3.78 20 30 50 15 −4.39 −14.173.48 50 20 30 33 −4.31 −12.59 3.42 60 20 20 35 −4.30 −11.99 3.41 20 3050 27 −4.28 −11.04 3.39 30 30 40 17 −4.22 −8.30 3.35 60 30 10 57 −4.21−10.01 3.34 40 30 30 5 −3.96 −17.67 3.14 10 20 70 9 −3.89 −13.76 3.09 4020 40 37 −3.82 −15.88 3.03 20 20 60 39 −3.78 −9.87 3.00 70 20 10 63−3.72 −8.08 2.95 50 30 20 1 −3.62 −11.69 2.87 50 20 30 29 −3.48 −13.362.76 30 20 50 53 −3.31 −7.48 2.63 10 40 50 19 −2.15 −4.54 1.71 20 40 4012 −1.76 −3.43 1.39 30 40 30 6 −1.71 −2.90 1.36 20 50 30 14 −1.69 −3.081.34 10 50 40 51 −1.67 −3.03 1.32 10 50 40 25 −1.66 −4.34 1.32 70 20 1036 −1.62 −2.66 1.28 50 40 10 4 −1.61 −2.90 1.28 40 40 20 7 −1.59 −4.651.26 60 20 20 49 −1.54 −2.53 1.22 50 40 10 10 −1.45 −2.45 1.15 20 50 3022 −1.37 −1.81 1.09 30 60 10 41 −1.37 −1.98 1.08 40 50 10 54 −1.29 −1.581.02 20 70 10 48 −1.26 −1.26 1.00 0 100 0 46 −1.24 −1.44 0.98 10 80 1030 −1.24 −1.79 0.98 40 50 10 34 −1.20 −1.74 0.95 40 50 10 60 −1.20 −1.880.95 30 50 20 38 −1.19 −1.87 0.95 30 50 20 58 −1.19 −1.69 0.94 20 60 2040 −1.19 −1.46 0.94 20 70 10 8 −1.17 −1.54 0.93 10 70 20 62 −1.15 −1.750.91 10 60 30 2 −1.13 −1.77 0.89 30 50 20

Example 2 Screening Catalysts for Electrocatalytic Activity

The catalysts compositions set forth in Tables A to C that weresynthesized on arrays according to the method set forth in Example 1were screened for electrochemical reduction of molecular oxygen to wateraccording to Protocol 1 (detailed below), to determine relativeelectrocatalytic activity against the internal and/or external platinumstandard. Additionally, the catalyst compositions set forth in Table Dthat were synthesized on arrays according to the method set forth inExample 1 were screened for electrochemical reduction of molecularoxygen to water according to Protocol 2 (detailed below) to determineelectrocatalytic activity.

In general, the array wafers were assembled into an electrochemicalscreening cell and a screening device established an electrical contactbetween the 64 electrode catalysts (working electrodes) and a 64-channelpotentiostat used for the screening. Specifically, each wafer array wasplaced into a screening device such that all 64 spots were facing upwardand a tube cell body that was generally annular and having an innerdiameter of about 2 inches (5 cm) was pressed onto the upward facingwafer surface. The diameter of this tubular cell was such that theportion of the wafer with the square electrode array formed the base ofa cylindrical volume while the contact pads were outside the cylindricalvolume. A liquid ionic solution (i.e., 0.5 M H₂SO₄ aqueous electrolyte)was poured into this cylindrical volume, and a common counter electrode(i.e., platinum gauze) and a common reference electrode (e.g.,mercury/mercury sulfate reference electrode (MMS)) were placed into theelectrolyte solution to close the electrical circuit.

A rotator shaft with blades was placed into the electrolyte to provideforced convection-diffusion conditions during the screening. Therotation rate was typically between about 300 to about 400 rpm.Depending on the screening experiment, either argon or pure oxygen wasbubbled through the electrolyte during the measurements. Argon served toremove O₂ gas in the electrolyte to simulate O₂-free conditions used forthe initial conditioning of the catalysts. The introduction of pureoxygen served to saturate the electrolyte with oxygen for the oxygenreduction reaction. During the screening, the electrolyte was maintainedat 60° C. and the rotation rate was constant.

Protocol 1: Three groups of tests were performed to screen the activityof the catalysts. The electrolyte was purged with argon for about 20minutes prior to the electrochemical measurements. The first group oftests comprised cyclic voltammetric measurements while purging theelectrolyte with argon. Specifically, the first group of testscomprised:

-   -   a. a potential sweep from open circuit potential (OCP) to about        +0.3 V to about −0.63 V and back to about +0.3 V at a rate of        about 20 mV/s;    -   b. seventy-five consecutive potential sweeps from OCP to about        +0.3 V to about −0.7 V and back to about +0.3 V at a rate of        about 200 mV/s; and    -   c. a potential sweep from OCP to about +0.3 V to about −0.63 V        and back to about +0.3 V at a rate of about 20 mV/s.        The shape of the cyclic voltammetric (CV) profile of the        internal Pt standard catalyst as obtained in test (c) was        compared to an external standard CV profile obtained from a Pt        thin film electrode that had been pretreated until a stable CV        was obtained. If test (c) resulted in a similar cyclic        voltammogram, the first group of experiments was considered        completed. If the shape of the cyclic voltammogram of test (c)        did not result in the expected standard Pt CV behavior,        tests (b) and (c) were repeated until the Pt standard catalyst        showed the desired standard voltammetric profile. In this way,        it was ensured that the Pt standard catalyst showed a stable and        well-defined oxygen reduction activity in subsequent        experiments. The electrolyte was then purged with oxygen for        approximately 30 minutes. The following second group of tests        was performed while continuing to purge with oxygen:    -   a. measuring the open circuit potential (OCP) for a minute;        then, the potential was stepped to −0.4 V, held for a minute,        and was then swept up to about +0.4 V at a rate of about 10        mV/s;    -   b. measuring the OCP for a minute; then applying a potential        step from OCP to about +0.1 V while measuring the current for        about 5 minutes; and    -   C. measuring the OCP for a minute; then applying a potential        step from OCP to about +0.2 V while monitoring the current for        about 5 minutes.        The third group of tests comprised a repeat of the second group        of tests after about one hour from completion of the second        group of tests. The electrolyte was continually stirred and        purged with oxygen during the waiting period. All the foregoing        test voltages are with reference to a mercury/mercury sulfate        (MMS) electrode. Additionally, an external platinum standard        comprising an array of 64 platinum electrodes was used to        monitor the tests to ensure the accuracy and consistency of the        oxygen reduction evaluation.

Protocol 2: Four groups of tests were performed to screen the activityof the catalysts. The first group is a pretreatment process, whereas theother three groups are identical sets of experiments in order to screenthe oxygen reduction activity as well as the current electrochemicalsurface area of the catalysts. The electrolyte was purged with argon forabout 20 minutes prior to the electrochemical measurements. The firstgroup of tests comprised cyclic voltammetric measurements while purgingthe electrolyte with argon. Specifically, the first group of testscomprised:

-   -   a. a potential sweep from open circuit potential (OCP) to about        +0.3 V to about −0.63 V and back to about +0.3 V at a rate of        about 20 mV/s;    -   b. fifty consecutive potential sweeps from OCP to about +0.3 V        to about −0.7 V and back to about +0.3 V at a rate of about 200        mV/s; and    -   c. a potential sweep from OCP to about +0.3 V to about −0.63 V        and back to about +0.3 V at a rate of about 20 mV/s.        After step (c) of the first group of tests, the electrolyte was        purged with oxygen for approximately 30 minutes. Then, the        following second group of tests was performed, which comprised a        test in an oxygen-saturated solution (i.e., test (a)), followed        by a test performed in an Ar-purged (i.e., an oxygen-free        solution, test (b)):    -   a. in an oxygen-saturated solution, the OCP was measured for a        minute; a potential step was then applied from OCP to about −0.4        V; this potential was held for approximately 30 seconds, and        then the potential was stepped to about +0.1 V while measuring        the current for about 5 minutes; and    -   b. after purging the electrolyte with Ar for approximately 30        minutes, a potential sweep was performed from open circuit        potential (OCP) to about +0.3 V to about −0.63 V and back to        about +0.3 V, at a rate of about 20 mV/s.        The third and fourth group of tests comprised a repeat of the        second group of tests after completion. All the foregoing test        voltages are with reference to a mercury/mercury sulfate (MMS)        electrode. Additionally, an external platinum standard        comprising an array of 64 platinum electrodes was used to        monitor the tests to ensure the accuracy and consistency of the        oxygen reduction evaluation.

The specific catalyst compositions set forth in Table A-D were preparedand screened in accordance with the above-described methods of Protocols1 (Tables A to C) or 2 (Table D), and the test results are set forththerein. The screening results in Tables A to C are for the third testgroup (steady state currents at +0.1 V MMS). The screening results inTable D were taken from the oxygen reduction measurements of the fourthgroup of tests (i.e., the last screening in an oxygen-saturatedsolution), the Ar-saturated steps serving as an evaluation of additionalcatalyst-related parameters, such as surface area over time.

The current value reported (End Current Density) is the result ofaveraging the last three current values of the chronoamperometric testnormalized for geometric surface area. It is to be noted, from theresults presented in these Tables, that numerous compositions exhibitedan oxygen reduction activity which exceeded, for example, the internalplatinum standard (see, e.g., the catalyst compositions corresponding toElectrode Numbers, for example: 34, 1 and 33 in Table A; 34 in Table B;1 and 17 in Table C; and 3, 21, 15, 33, 35, 27,17, 57, 5, 9, 37, 39, 63,1, 29, 53, 19, 12, 6, 14, 51, 25, 36, 4, 7, 49, 10, 22, 41 and 54 inTable D).

Example 3 Synthesis of Supported Catalysts

The synthesis of multiple Pt—Cu—W catalyst compositions (see Table E,Parts 1-4, Target Catalyst Comp., infra) on carbon support particles wasattempted according to different process conditions, in order toevaluate the performance of the catalysts while in a state that istypically used in a fuel cell. To do so, the catalyst components weredeposited or precipitated on supported platinum powder (i.e., platinumnanoparticles supported on carbon black particles). Platinum supportedon carbon black is commercially available from companies such as JohnsonMatthey, Inc., of New Jersey and E-Tek Div. of De-Nora, N.A., Inc., ofSomerset, N.J. Such supported platinum powder is available with a widerange of platinum loading. The supported platinum powder used in thisExample had a nominal platinum loading of about 20 or about 40 percentby weight, a platinum surface area of between about 150 and about 170m²/g (determined by CO adsorption), a combined carbon and platinumsurface area between about 350 and about 400 m²/g (determined by N₂adsorption), and an average particle size of less than about 0.5 mm(determined by a sizing screen).

The catalyst compositions of Table E (Parts 1-4, infra) were formed oncarbon support particles using a freeze-drying precipitation method. Thefreeze-drying method comprised forming an initial solution comprisingthe desired metal atoms in the desired concentrations. Each of thesupported catalysts were prepared in an analogous manner, withvariations being made in the amounts of metal-containing compounds usedtherein. For example, to prepare the target Pt₂₀Cu₂₀W₆₀ catalystcomposition (e.g., HFC 1295), having a final nominal platinum loading ofabout 12.00 percent by weight, 0.472 ml of a 0.25 M aqueous solution ofCu(NO₃)₂.2.5H₂O and 0.591 ml of a 0.05 M aqueous solution of(NH₄)₆W₁₂O₃₉.5H₂O were mixed with about 1.937 ml H₂O, forming a clearsolution. To prepare the target Pt₁₅Cu₃₅W₅₀ catalyst composition (e.g.,HFC 1309), having a final nominal platinum loading of about 11.00percent by weight, 1.102 ml of a 0.25 M aqueous solution ofCu(NO₃)₂.2.5H₂O and 0.656 ml of a 0.05 M aqueous solution of(NH₄)₆W₁₂O₃₉.5H₂O were mixed with about 1.242 ml H₂O, forming a clearsolution. The solutions were introduced into quartz vials, eachcontaining about 0.100 g of supported platinum powder having a nominalplatinum loading of about 19.2 percent by weight, resulting in a blacksuspension. The suspensions were homogenized by immersing a probe of aBRANSON SONIFIER 150 into the vials and sonicating the mixtures forabout 1.5 minutes at a power level of 3. The vials containing thehomogenized suspensions were then immersed in a liquid nitrogen bath forabout 3 minutes to solidify the suspensions. The solid suspensions werethen freeze-dried for about 24 hours using a LABCONCO FREEZE DRY SYSTEM(Model 79480) to remove the solvent. The tray and the collection coil ofthe freeze dryer were maintained at about 27° C. and about −49° C.,respectively, while evacuating the system (the pressure was maintainedat about 0.05 mbar). After freeze-drying, the vials contained a powdercomprising the supported platinum powder, as well as tungsten and coppercompounds deposited thereon.

The recovered powders were then subjected to a heat treatment to reducethe constituents therein to their metallic state, and to fully orpartially alloy the metals with each other and the platinum on thecarbon black particles. One particular heat treatment comprised heatingthe powders in a quartz flow furnace with an atmosphere comprising about6% H₂ and 94% Ar using a temperature profile of room temperature toabout 90° C. at a rate of about 5° C./minute; holding at about 90° C.for 2 hours; increasing the temperature to about 200° C. at a rate of 5° C./minute; holding at about 200° C. for two hours; increasing thetemperature at a rate of about 5° C./minute to a maximum temperature of,for example, about 600, 700, 800, 900, or 950° C.; holding at themaximum temperature for a duration of about 1.2, 2, 6, 7 or 10 hours (asindicated in Table E, Parts 1-4, infra); and, then cooling down to roomtemperature.

In order to determine the actual composition of the supported catalysts,the differently prepared catalysts (e.g., by composition variation or byheat treatment variation) were subjected to EDS (Electron DispersiveSpectroscopy) elemental analysis. For this technique, the sample powderswere compressed into 6 mm diameter pellets with a thickness of about 1mm. The target composition and actual composition for certain supportedcatalysts are set forth in Table E (Parts 1-4).

TABLE E Part 1 Actual Target Catalyst Target Catalyst Time at MaxCatalyst Actual Catalyst Actual Powder Name Comp. Comp. Target Catalyst*W Max Alloying Alloying Temp Comp. Comp. Catalyst (HFC) Pt Cu Comp. WPrecursor Temp (° C.) (hrs) Pt Cu Comp. W 10 100 0 0 100 0 0 567 40 5010 A 700 7 568 30 10 60 A 700 7 572 40 50 10 A 900 2 573 30 10 60 A 9002 652 30 60 10 A 900 12 1033 30 10 60 A 700 7 39 14 47 1034 30 15 55 A700 7 1035 25 15 60 A 700 7 35 33 33 1036 35 10 55 A 700 7 1037 30 5 65A 700 7 1038 25 20 55 A 700 7 1039 35 15 50 A 700 7 1040 20 15 65 A 7007 1042 30 20 50 A 700 7 1043 20 20 60 A 700 7 1044 40 10 50 A 700 7 4916 34 1046 25 25 50 A 700 7 1047 20 25 55 A 700 7 1048 35 20 45 A 700 71049 25 10 65 A 700 7 1050 35 5 60 A 700 7 1051 40 5 55 A 700 7 1052 255 70 A 700 7 1053 20 10 70 A 700 7 1055 15 20 65 A 700 7 1056 40 15 45 A700 7 1102 15 15 70 A 700 7 21 14 65 1103 45 5 50 A 700 7 1104 30 25 45A 700 7 1105 15 25 60 A 700 7 1106 20 30 50 A 700 7 25 26 49 1107 40 2040 A 700 7 1108 10 20 70 A 700 7 1109 25 30 45 A 700 7 1110 45 10 45 A700 7 1111 15 10 75 A 700 7 1112 15 30 55 A 700 7 1113 45 15 45 A 700 71147 30 10 60 B 700 7 35 12 52 1148 30 15 55 B 700 7 35 18 47 1149 25 1560 B 700 7 29 16 55 1150 35 10 55 B 700 7 41 10 49 1151 30 5 65 B 700 71152 25 20 55 B 700 7 1153 25 10 65 B 700 7 1154 35 5 60 B 700 7 45 7 481155 40 5 55 B 700 7 1156 25 5 70 B 700 7 1157 35 15 50 B 700 7 1158 2015 65 B 700 7 1294 20 10 70 B 700 7 1295 20 20 60 B 700 7 25 25 51 129630 20 50 B 700 7 1297 40 10 50 B 700 7 44 7 48 1298 20 5 75 B 700 7 129920 25 55 B 700 7 1300 25 25 50 B 700 7 1301 35 20 45 B 700 7 1302 15 2560 B 700 7 1303 30 25 45 B 700 7 1304 45 10 45 B 700 7 1305 20 30 50 B700 7 1306 25 30 45 B 700 7 1307 35 25 40 B 700 7 1308 45 15 40 B 700 71309 15 35 50 B 700 7 20 28 52 1310 15 15 70 B 700 7 1311 15 20 65 B 7007 1312 40 15 45 B 700 7 42 13 44 1313 15 10 75 B 700 7 26 13 61 1314 4020 40 B 700 7 1315 15 30 55 B 700 7 1316 20 35 45 B 700 7 1317 25 35 40B 700 7 30 30 42 1368 32 10 58 B 700 7 36 8 56 1369 32 12 56 B 700 7 3112 57 1370 34 8 58 B 700 7 1371 34 10 56 B 700 7 32 9 59 1372 36 10 54 B700 7 39 9 52 1373 36 12 52 B 700 7 1374 38 8 54 B 700 7 1375 38 10 52 B700 7 1376 34 12 54 B 700 7 35 11 54 1377 36 8 56 B 700 7 1378 38 12 50B 700 7 1379 40 10 50 B 700 7 1484 30 10 60 B 700 7 1485 30 15 55 B 7007 1486 32 10 58 B 700 7 1487 32 12 56 B 700 7 1488 34 8 58 B 700 7 148934 10 56 B 700 7 1490 35 5 60 B 700 7 1491 35 10 55 B 700 7 1541 30 1060 B 700 7 1542 30 15 55 B 700 7 1543 32 10 58 B 700 7 1544 32 12 56 B700 7 1545 34 8 58 B 700 7 1546 34 10 56 B 700 7 1547 35 5 60 B 700 71548 35 10 55 B 700 7 1573 30 10 60 B 700 7 34 9 57 1574 30 15 55 B 7007 34 16 50 1575 32 10 58 B 700 7 1576 32 12 56 B 700 7 1577 34 8 58 B700 7 1578 34 10 56 B 700 7 1579 35 5 60 B 700 7 1580 35 10 55 B 700 740 11 49 1767 35 10 55 B 600 2 35 12 53 1768 35 10 55 B 650 2 35 12 531769 35 10 55 B 750 2 35 12 53 1770 35 10 55 B 925 2 35 12 53 1771 35 1055 B 600 10 35 12 53 1772 35 10 55 B 700 10 35 12 53 1773 35 10 55 B 82510 35 12 53 1774 35 10 55 B 925 10 35 12 53 1835 35 10 55 B 750 10 37 756 1836 35 10 55 B 650 7 37 9 54 1837 35 10 55 B 700 2 37 9 54 1838 3510 55 B 650 10 37 9 54 1839 35 10 55 B 600 14 37 10 53 1840 35 10 55 B675 10 37 9 54 1841 35 10 55 B 700 6 37 9 54 1842 35 10 55 B 700 14 37 954 1856 35 10 55 B 700 6 36 12 51 *Note that “A” and “B” for “WPrecursor” indicates para-tungstate and meta-tungstate, respectively.Part 2 Actual Pt Pt Mass Catalyst Mass Catalyst Comp. Target Pt LoadingBefore Activity at Relative Activity at Powder Name Catalyst Comp. afterScreening Catalyst Comp. Loading Screening +0.15 V MMS peformance at+0.15 V MMS (HFC) after Screening Pt Cu after Screening W (wt %) (wt %)(mA/mg Pt) +0.15 V MMS (mA/mg) 10 100 0 0 37.8 37.8 128.82 1.00 48.70567 17 367.30 2.85 62.44 568 13.9 450.52 3.50 62.62 572 17 271.28 2.1146.12 573 13.9 106.10 0.82 14.75 652 13.9 225.94 1.75 31.41 1033 42 1642 13.89 13.00 464.18 3.85 64.45 1034 14.09 392.27 3.05 55.26 1035 47 1143 13.05 12.60 533.29 4.29 69.57 1036 14.74 362.06 2.81 53.38 1037 13.69337.67 2.62 46.23 1038 13.26 413.55 3.21 54.83 1039 14.94 287.24 2.2342.91 1040 11.74 356.36 2.77 41.85 1042 14.29 271.63 2.11 38.83 104311.96 404.84 3.14 48.42 1044 60 7 34 15.46 16.75 461.96 3.31 71.43 104613.48 344.97 2.68 46.50 1047 12.18 425.51 3.30 51.85 1048 15.14 325.632.53 49.29 1049 12.84 380.07 2.95 48.80 1050 14.56 311.30 2.42 45.311051 15.28 284.78 2.21 43.51 1052 12.64 312.77 2.43 39.53 1053 11.53350.58 2.72 40.44 1055 10.28 332.49 2.58 34.18 1056 15.65 270.95 2.1042.40 1102 50 7 43 10.07 11.99 479.02 3.21 48.23 1103 15.89 265.55 2.0642.21 1104 14.51 346.04 2.69 50.20 1105 10.50 272.89 2.12 28.66 1106 4610 45 12.42 13.53 462.38 3.29 57.42 1107 15.84 351.62 2.73 55.69 11088.03 257.95 2.00 20.71 1109 13.71 341.99 2.65 46.88 1110 16.07 286.672.23 46.06 1111 9.86 294.69 2.29 29.07 1112 10.74 405.70 3.15 43.55 111316.25 253.62 1.97 41.21 1147 44 8 49 13.89 14.88 325.98 2.53 45.26 114847 8 45 14.09 15.06 376.88 2.93 53.09 1149 46 7 47 13.05 13.94 397.583.09 51.87 1150 47 9 44 14.74 15.59 401.81 3.12 59.24 1151 13.69 342.502.66 46.89 1152 13.26 366.93 2.85 48.65 1153 12.84 285.99 2.22 36.721154 48 5 46 14.56 15.96 285.20 2.21 41.51 1155 15.28 253.23 1.97 38.691156 12.64 260.70 2.02 32.95 1157 14.94 291.04 2.26 43.48 1158 11.74363.02 2.82 42.63 1294 11.5 338.81 2.63 39.11 1295 49 7 44 12.0 13.41468.92 3.64 56.00 1296 14.3 351.69 2.73 50.29 1297 55 6 40 15.5 15.90334.94 2.60 51.88 1298 11.3 360.71 2.80 40.90 1299 12.2 369.73 2.8745.05 1300 13.5 309.18 2.40 41.80 1301 15.1 276.97 2.15 41.80 1302 10.5305.32 2.37 32.06 1303 14.5 338.81 2.63 49.22 1304 16.1 257.65 2.0041.40 1305 12.4 314.33 2.44 39.11 1306 13.7 329.79 2.56 45.15 1307 15.3237.04 1.84 36.41 1308 16.3 257.65 2.00 42.10 1309 48 9 43 11.0 12.33432.85 3.36 47.46 1310 10.1 347.83 2.70 35.35 1311 10.3 383.90 2.9839.51 1312 53 6 40 15.7 15.88 373.59 2.90 58.45 1313 47 7 46 9.9 13.19403.22 3.13 39.73 1314 15.8 288.57 2.24 45.79 1315 10.7 409.66 3.1843.91 1316 12.7 445.73 3.46 56.35 1317 48 8 44 13.9 14.59 396.78 3.0855.32 1368 53 9 38 14.3 14.82 373.59 2.90 53.28 1369 49 7 44 14.3 14.15392.92 3.05 56.24 1370 14.51 313.36 2.43 45.46 1371 53 9 38 14.59 14.21407.63 3.16 59.45 1372 49 7 44 14.90 15.29 371.52 2.88 55.35 1373 14.97320.64 2.49 48.01 1374 15.11 318.80 2.47 48.19 1375 15.19 310.09 2.4147.10 1376 52 8 40 14.66 14.78 410.77 3.19 60.23 1377 14.82 333.20 2.5949.39 1378 15.26 341.77 2.65 52.17 1379 15.46 332.01 2.58 51.33 148413.89 217.18 1.69 30.16 1485 14.09 252.08 1.96 35.51 1486 14.25 203.421.58 28.99 1487 14.33 225.54 1.75 32.31 1488 14.51 259.79 2.02 37.691489 14.59 211.41 1.64 30.83 1490 14.56 214.35 1.66 31.20 1491 14.74232.29 1.80 34.25 1541 13.89 253.48 1.97 35.20 1542 14.09 287.25 2.2340.46 1543 14.25 226.10 1.76 32.22 1544 14.33 302.00 2.34 43.27 154514.51 255.18 1.98 37.02 1546 14.59 263.83 2.05 38.48 1547 14.56 264.072.05 38.44 1548 14.74 269.46 2.09 39.73 1573 49 4 47 13.89 14.55 422.823.28 58.71 1574 51 4 45 14.09 14.82 338.49 2.63 47.68 1575 14.25 323.152.51 46.04 1576 14.33 398.50 3.09 57.09 1577 14.51 423.85 3.29 61.491578 14.59 396.21 3.08 57.79 1579 14.56 392.25 3.04 57.09 1580 52 5 4314.74 15.50 404.29 3.14 59.61 1767 14.74 351.42 2.73 51.80 1768 58 4 3914.74 14.82 332.79 2.58 49.05 1769 51 49 14.74 14.82 304.19 2.36 44.841770 54 46 14.74 14.82 296.32 2.30 43.68 1771 56 4 40 14.74 14.82 365.742.84 53.91 1772 49 5 46 14.74 14.82 433.25 3.36 63.86 1773 55 45 14.7414.82 279.54 2.17 41.20 1774 59 1 42 14.74 14.82 284.42 2.21 41.92 183544 3 52 14.74 14.93 294.74 2.29 43.46 1836 51 4 45 14.74 15.01 390.183.03 57.53 1837 48 3 49 14.74 15.01 352.51 2.74 51.97 1838 48 3 48 14.7415.01 348.02 2.70 51.31 1839 49 7 45 14.74 15.05 411.73 3.20 60.71 184047 1 52 14.74 15.01 346.91 2.69 51.15 1841 44 2 54 14.74 15.01 381.972.96 56.32 1842 48 3 49 14.74 15.01 397.56 3.09 58.62 1856 47 6 47 14.7415.03 466.35 3.62 68.74 Part 3 [Washed Powders] Target Target TargetCatalyst Catalyst Catalyst Comp. Comp Comp Catalyst Catalyst CatalystPrecursor before before before Comp. after Comp. after Comp. after Namewashing washing washing washing washing washing Acid Conc./ Wash Temp.Wash Time # of Name (HFC) (HFC) at % Pt at % Cu at % W at % Pt at % Cuat % W Identity (° C.) (min) washes 1447 1154 35 5 60 59 5 36 1 M HClO₄90 60 2 1448 1150 35 10 55 60 9 31 1 M HClO₄ 90 60 2 1125 1033 30 10 6036 8 56 5 M H₂SO₄ 25 60 2 1126 1035 25 15 60 31 9 60 5 M H₂SO₄ 25 60 2Part 4 [Washed Powders, Continued] Pt Mass Catalyst Corrosion CatalystCatalyst Catalyst Pt Activity at Relative Mass Activity PrecursorDistance Comp. after Comp. after Comp. after Pt Loading Loading +0.15 Vperformance at +0.15 V Name Name before/after screening screeningscreening before wash after wash MMS at +0.15 V MMS (HFC) (HFC)screening at % Pt at % Cu at % W (wt %) (wt %) (mA/mg Pt) MMS (mA/mg)1447 1154 18.00 48 2 50 14.56 17.21 267.96 2.08 39.01 1448 1150 39.90 345 61 14.74 17.41 216.00 1.68 31.84 1125 1033 14.35 47 6 47 13.89 14.82315.41 2.45 43.81 1126 1035 8.83 38 4 58 13.05 14.03 342.77 2.66 44.73

Example 4 Evaluation of Catalytic Activity of Supported Catalysts

The supported alloy catalysts set forth in Table E (i.e., Table E, Parts1-4) and formed according to Example 3 were subjected to electrochemicalmeasurements to evaluate their activities. For the evaluation, thesupported catalysts were applied to a rotating disk electrode (RDE) asis commonly used in the art (see, Rotating Disk Electrode Measurementson the CO Tolerance of a High-surface Area Pt/Vulcan Carbon Fuel CellElectrocatalyst, Schmidt et al., Journal of the Electrochemical Society(1999), 146(4), 1296-1304; and, Characterization of High Surface-AreaElectrocatalysts using a Rotating Disk Electrode Configuration, Schmidtet al., Journal of the Electrochemical Society (1998), 145(7),2354-2358). Rotating disk electrodes are a relatively fast and simplescreening tool for evaluating supported catalysts with respect to theirintrinsic electrolytic activity for oxygen reduction (e.g., the cathodicreaction of a fuel cell).

The rotating disk electrodes were prepared by depositing anaqueous-based ink that comprises the supported catalyst and a NAFION™solution on a glassy carbon disk. The concentration of catalyst powderin the NAFION™ solution was about 1 mg/ml. The NAFION™ solutioncomprised the perfluorinated ion-exchange resin, lower aliphaticalcohols and water, wherein the concentration of resin was about 5percent by weight. The NAFION™ solution is commercially available fromALDRICH as product number 27,470-4. The glassy carbon electrodes were 5mm in diameter and were polished to a mirror finish. Glassy carbonelectrodes are commercially available, for example, from Pine InstrumentCompany of Grove City, Pa. For each electrode, an aliquot of 10 μL ofthe catalyst suspension was deposited on to the glassy carbon disk andallowed to dry at a temperature between about 60 and 70° C. Theresulting layer of NAFION™ and catalyst was less than about 0.2 μmthick. This method produced slightly different platinum loadings foreach electrode made with a particular suspension, but the variation wasdetermined to be less than about 10 percent by weight.

After being dried, each rotating disk electrode was immersed into anelectrochemical cell comprising an aqueous 0.5 M H₂SO₄ electrolytesolution maintained at room temperature. Before performing anymeasurements, the electrochemical cell was purged of oxygen by bubblingargon through the electrolyte for about 20 minutes. All measurementswere taken while rotating the electrode at about 2000 rpm, and themeasured current densities were normalized either to the glassy carbonsubstrate area or to the platinum loading on the electrode. Two groupsof tests were performed to screen the activity of the supportedcatalysts. The first group of tests comprised cyclic voltammetricmeasurements while purging the electrolyte with argon. Specifically, thefirst group comprised:

-   -   a. two consecutive potential sweeps starting from OCP to about        +0.35V then to about −0.65V and back to OCP at a rate of about        50 mV/s;    -   b. two hundred consecutive potential sweeps starting from OCP to        about +0.35V then to about −0.65V and back to OCP at a rate of        about 200 mV/s; and    -   c. two consecutive potential sweeps starting from OCP to about        +0.35V then to about −0.65V and back to OCP at a rate of about        50 mV/s.        The second test comprised purging with oxygen for about 15        minutes followed by a potential sweep test for oxygen reduction        while continuing to purge the electrolyte with oxygen.        Specifically, potential sweeps from about −0.45 V to +0.35 V        were performed at a rate of about 5 mV/s to evaluate the initial        activity of the catalyst as a function of potential and to        create a geometric current density plot. The catalysts were        evaluated by comparing the diffusion corrected activity at        0.15 V. All the foregoing test voltages are with reference to a        mercury/mercury sulfate electrode. Also, it is to be noted that        the oxygen reduction measurements for a glassy carbon RDE        without a catalyst did not show any appreciable activity within        the potential window.

The above-described supported catalyst compositions were evaluated inaccordance with the above-described method and the results are set forthin Table E (Parts 1-4). It is to be noted from the results presentedtherein that substantially all of the carbon supported catalystcompositions exhibited an oxygen reduction activity which exceeded, forexample, the carbon supported platinum standard (see, e.g., samples 568,1035, 1309, 1577, 1772 and 1856).

The results of the evaluation indicate, among other things, that asupported catalyst of the present invention may be produced usingdifferent process temperatures and durations. It is to be noted,however, that it may take numerous iterations to develop a set ofparameters for producing a particular catalyst composition. Alsoevidenced by the data is that activity may be adjusted by changes in theprocessing conditions.

Further, without being held to a particular theory, it is presentlybelieved that differences in activity for similar catalyst compositionsmay be due to several factors, such as homogeneity (e.g., an alloy, asdefined herein, may have regions in which the constituent atoms show apresence or lack of order, i.e., regions of solid solution within anordered lattice, or some type of superstructure), changes in the latticeparameter due to changes in the average size of component atoms, changesin particle size, and changes in crystallographic structure/symmetry.The ramifications of synthesis, structure and symmetry changes are oftendifficult to predict.

An interpretation of XRD analyses for a few of the foregoing supportedcatalysts is set forth below. It is to be noted, however, thatinterpretation of XRD analyses can be subjective, and therefore, thefollowing conclusions are not intended to be limiting.

Pt₃₅Cu₁₀W₅₅ (see, for example, sample HFC 1770): According to Table E,sample HFC 1770 was annealed at 900° C. for 2 hours. Assuming that theface-centered-cubic structure (fcc) of Pt and/or Cu was maintained, thelattice constant of HFC 1770, based on the targeted stoichiometry, waspredicted to increase slightly as compared to pure platinum (given thatthe metallic radius of tungsten is larger than that of platinum). Infact, XRD measurements of HFC 1770 indicated that the lattice constantof this material increased by approximately 1.8%. The particle size wasestimated to be approximately 2.4 nm, using the known Scherrer/Warrenequation.

Pt₃₅Cu₁₀W₅₅ (see, for example, sample HFC 1772): According to Table E,sample HFC 1772 was annealed at 700° C. for 10 hours. Assuming that theface-centered-cubic structure (fcc) of Pt and/or Cu was maintained, thelattice constant of HFC 1772, based on the targeted stoichiometry, waspredicted, as above, to increase slightly as compared to pure platinum.In fact, XRD measurements of HFC 1772 indicated that this materialprimarily crystallized in the body-centered-cubic (bcc) structure of W.Some fcc material was also present. The superposition of the bcc and fcccomponents made the determination of particle size difficult.

In view of the foregoing, for a particular catalyst composition, adetermination of the optimum conditions is preferred to produce thehighest activity for that particular composition. In fact, for certaincatalyst compositions, different structural characteristics may definewhat exactly is described as a good catalyst. These characteristics mayinclude differences in the composition (as viewed by lattice parameter),crystallinity, crystallographic structure, ordering and/or particlesize. These characteristics are not easily predictable and may depend ona complex interplay between starting materials, synthesis method,synthesis temperature and composition. For example, the startingmaterials used to synthesize the catalyst alloy may play a role in theactivity of the synthesized catalyst alloy. Specifically, usingsomething other than a metal nitrate salt solution to supply the metalatoms may result in different activities. Additionally, alternative Ptsources may be employed. Freeze-drying and heat treatment parameterssuch as atmosphere, time, temperature, etc. may also requireoptimization. This optimization may be compositionally dependent.Additionally, this optimization may involve balancing competingphenomena. For example, increasing the heat treatment temperature isgenerally known to improve the reduction of a metal salt to a metal,which typically increases activity; however, this also tends to increasethe size of the catalyst alloy particle and decrease surface area, whichdecreases electrocatalytic activity. In this case, increasing the heattreatment temperature also appears to influence the crystallographicstructure of the resulting alloy.

Example 5 Washing of Catalyst Composition Precursor

A catalyst precursor composition may be washed according to thefollowing procedure: 100 mg of a powder catalyst composition precursor(e.g., Sample HFC 1856, Pt₃₅Cu₁₀W₅₅) is placed into a 20 ml glass vial,followed by the slow addition (over a 5 to 10 second period of time, inorder to allow sufficient time for the acid to wet the powder) of 15 mlof a 1 M HClO₄ acid solution. This mixture is placed on a hot platewhich had been previously calibrated to raise the temperature of themixture to 90-95° C. (the vial in which the mixture had been placedbeing capped, but not tightly so that any boiling which occurs takesplace without a build-up of pressure therein). After 1 hour under atthese conditions, the mixture is filtered through filter paper. Thefiltered cake is washed repeatedly with a large excess of water.

Following this initial, single wash cycle, the isolated filter cake isput back into a new vial with another 15 ml of 1 M HClO₄ acid solution.After enough stirring is performed to break apart the filter cake, themixture is put back on the hot plate at 90-95° C. for 1 hour. Themixture is then filtered and washed with water once again. The resultingcake is dried at 90° C. for 48 hours.

It is to be understood that the above description is intended to beillustrative and not restrictive. Many embodiments will be apparent tothose of skill in the art upon reading the above description. The scopeof the invention should therefore be determined not with reference tothe above description alone, but should be determined with reference tothe claims and the full scope of equivalents to which such claims areentitled.

When introducing elements of the present invention or an embodimentthereof, the articles “a”, “an”, “the” and “said” are intended to meanthat there are one or more of the elements. The terms “comprising”,“including” and “having” are intended to be inclusive and mean thatthere may be additional elements other than the listed elements.

The recitation of numerical ranges by endpoints includes all numberssubsumed within that range. For example, a range described as beingbetween 1 and 5 includes 1, 1.6, 2, 2.8, 3, 3.2, 4, 4.75, and 5.

1. A composition comprising platinum (as platinum metal, platinum oxide,platinum carbide and/or a platinum salt), copper (as copper metal,copper oxide, copper carbide and/or a copper salt) and tungsten (as atleast tungsten oxide), wherein the sum of the concentrations of saidplatinum (as platinum metal, platinum oxide, platinum carbide and/or aplatinum salt), said copper (as copper metal, copper oxide, coppercarbide and/or a copper salt), and said tungsten (as at least tungstenoxide) is greater than 90 atomic percent.
 2. The composition of claim 1wherein said sum is greater than 92 atomic percent.
 3. The compositionof claim 1 wherein the concentration of said platinum (as platinummetal, platinum oxide, platinum carbide and/or platinum salt) is atleast about 10 atomic percent and less than about 80 atomic percent. 4.The composition of claim 1 wherein the concentration of said tungsten(as at least tungsten oxide) is at least about 10 atomic percent andless than about 80 atomic percent.
 5. The composition of claim 1 whereinthe concentration of said copper (as copper metal, copper oxide, coppercarbide and/or copper salt) is at least about 1 atomic percent and lessthan about 60 atomic percent.
 6. The composition of claim 1 wherein (i)the sum of the concentrations of said platinum (as platinum metal,platinum oxide, platinum carbide and/or platinum salt), said copper (ascopper metal, copper oxide, copper carbide and/or copper salt) and saidtungsten (as at least tungsten oxide) is greater than 95 atomic percent,and (ii) the concentration of said platinum (as platinum metal, platinumoxide, platinum carbide and/or platinum salt) is greater than about 20atomic percent and less than about 50 atomic percent.
 7. The compositionof claim 1 wherein (i) the sum of the concentrations of said platinum(as platinum metal, platinum oxide, platinum carbide and/or platinumsalt), said copper (as copper metal, copper oxide, copper carbide and/orcopper salt) and said tungsten (as at least tungsten oxide) is greaterthan 95 atomic percent, and (ii) the concentration of said tungsten (asat least said tungsten oxide) is greater than about 40 atomic percentand less than about 80 atomic percent.
 8. The composition of claim 1wherein (i) the sum of the concentrations of said platinum (as platinummetal, platinum oxide, platinum carbide and/or platinum salt), saidcopper (as copper metal, copper oxide, copper carbide and/or coppersalt) and said tungsten (as at least tungsten oxide) is greater than 95atomic percent, and (ii) the concentration of copper (as copper metal,copper oxide, copper carbide and/or copper salt) is greater than about 2atomic percent and less than about 25 atomic percent.
 9. The compositionof claim 1 wherein the composition consists essentially of said platinum(as platinum metal, platinum oxide, platinum carbide and/or platinumsalt), said copper (as copper metal, copper oxide, copper carbide and/orcopper salt) and said tungsten (as at least tungsten oxide).
 10. Thecomposition of claim 1 wherein the concentration of said copper (ascopper metal, copper oxide, copper carbide, and/or copper salt) isgreater than about 1 atomic percent.
 11. The composition of claim 1wherein the concentration of said tungsten (as at least tungsten oxide)is greater than about 1 atomic percent.
 12. The composition of claim 1wherein the concentration of said platinum (as platinum metal, platinumoxide, platinum carbide, and/or platinum salt) is greater than about 1atomic percent.
 13. The composition of claim 1, wherein the copperpresent therein has an average oxidation state of about zero.
 14. Asupported electrocatalyst powder for use in electrochemical reactordevices, the supported electrocatalyst powder comprising the compositionof claim 1 on electrically conductive supports.
 15. A compositioncomprising platinum (as platinum metal, platinum oxide, platinum carbideand/or a platinum salt), copper (as copper metal, copper oxide, coppercarbide and/or a copper salt) and tungsten (as at least tungsten oxide),wherein the concentration of said tungsten (as at least tungsten oxide)is greater than 40 atomic percent.
 16. The composition of claim 15,wherein the copper present therein has an average oxidation state ofabout zero.
 17. A supported electrocatalyst powder for use inelectrochemical reactor devices, the supported electrocatalyst powdercomprising the composition of claim 15 on electrically conductivesupports.
 18. A composition comprising platinum (as platinum metal,platinum oxide, platinum carbide and/or a platinum salt), copper (ascopper metal, copper oxide, copper carbide and/or a copper salt) andtungsten (as at least tungsten oxide), wherein the concentration of saidplatinum (as platinum metal, platinum oxide, platinum carbide and/orplatinum salt) is at least 30 atomic percent.
 19. The composition ofclaim 18, wherein the copper present therein has an average oxidationstate of about zero.
 20. A supported electrocatalyst powder for use inelectrochemical reactor devices, the supported electrocatalyst powdercomprising the composition of claim 18 on electrically conductivesupports.
 21. A composition comprising platinum (as platinum metal,platinum oxide, platinum carbide and/or a platinum salt), copper (ascopper metal, copper oxide, copper carbide and/or a copper salt) andtungsten (as at least tungsten oxide), wherein the concentration of saidcopper (as copper metal, copper oxide, copper carbide and/or copper) isless than 20 atomic percent.
 22. The composition of claim 21, whereinthe copper present therein has an average oxidation state of about zero.23. A supported electrocatalyst powder for use in electrochemicalreactor devices, the supported electrocatalyst powder comprising thecomposition of claim 21 on electrically conductive supports.
 24. Acomposition comprising platinum (as platinum metal, platinum oxide,platinum carbide and/or a platinum salt), copper (as copper metal,copper oxide, copper carbide and/or a copper salt) and tungsten (as atleast tungsten oxide), wherein said composition has a body-centeredcubic lattice structure.
 25. The composition of claim 24 wherein theconcentration of said tungsten (as at least tungsten oxide) exceeds thesum of the concentrations of said platinum (as platinum metal, platinumoxide, platinum carbide, and/or platinum salt) and said copper (ascopper metal, copper oxide, copper carbide, and/or copper salt).
 26. Thecomposition of claim 24, wherein the copper present therein has anaverage oxidation state of about zero.
 27. A supported electrocatalystpowder for use in electrochemical reactor devices, the supportedelectrocatalyst powder comprising the composition of claim 24 onelectrically conductive supports.
 28. A composition comprising platinum(as platinum metal, platinum oxide, platinum carbide and/or a platinumsalt), copper (as copper metal, copper oxide, copper carbide and/or acopper salt) and tungsten (as at least tungsten oxide), wherein thecomposition has a face-centered-cubic lattice structure.
 29. Thecomposition of claim 28 wherein the concentration of said tungsten (asat least tungsten oxide) exceeds the sum of the concentrations of saidplatinum (as platinum metal, platinum oxide, platinum carbide, and/orplatinum salt) and said copper (as copper metal, copper oxide, coppercarbide, and/or copper salt).
 30. The composition of claim 28, whereinthe copper present therein has an average oxidation state of about zero.31. A supported electrocatalyst powder for use in electrochemicalreactor devices, the supported electrocatalyst powder comprising thecomposition of claim 28 on electrically conductive supports.